CA1070086A - Lime recovery process - Google Patents
Lime recovery processInfo
- Publication number
- CA1070086A CA1070086A CA254,350A CA254350A CA1070086A CA 1070086 A CA1070086 A CA 1070086A CA 254350 A CA254350 A CA 254350A CA 1070086 A CA1070086 A CA 1070086A
- Authority
- CA
- Canada
- Prior art keywords
- lime
- percent
- calcium hypochlorite
- slurry
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/04—Hypochlorous acid
- C01B11/06—Hypochlorites
- C01B11/064—Hypochlorites of alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/03—Preparation from inorganic peroxy compounds, e.g. from peroxysulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
- D06L4/22—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents
- D06L4/23—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents using hypohalogenites
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An improved process for precipitating and recovering lime by reacting an aqueous solution of calcium hypochlorite with an alkaline compound is described. The pH of the resulting lime slurry is maintained in the range from about 11 to about 13.5, whereby hemi-basic calcium hypo-chlorite crystals form in the slurry, and when the slurry is filtered or otherwise separated to recover the lime, an improved filtration rate is obtained. In addition, washing of the lime cake to remove impurities such as sodium chloride is easily accomplished because of the ease of separating wash water in the presence of the hemi-basic calcium hypochlorite crystals.
An improved process for precipitating and recovering lime by reacting an aqueous solution of calcium hypochlorite with an alkaline compound is described. The pH of the resulting lime slurry is maintained in the range from about 11 to about 13.5, whereby hemi-basic calcium hypo-chlorite crystals form in the slurry, and when the slurry is filtered or otherwise separated to recover the lime, an improved filtration rate is obtained. In addition, washing of the lime cake to remove impurities such as sodium chloride is easily accomplished because of the ease of separating wash water in the presence of the hemi-basic calcium hypochlorite crystals.
Description
C9Q~il6 C-6645 This invention relates to the recovery of lime from calcium hypochlorite solutions.
A variety of processes and modifications are known in the art for manufacturing calcium hypochlorite.
U.S. Patent No. 1,713,669, issued to Rob rt B.
MacMullin et al on May 21, 1929, discloses a process in which an aqueous slurry of lime is chlorinated, solid impurities are removed, and caustic and chlorine are added to produce calcium hypochlorite and alkali chloride.
The concentration of the calcium hypochlorite-alkali chloride mixture is kept dilute so that the alkali chloride remains in solution while the calcium hypochlorite dihydrate is precipitated. After separation of the solid calcium hypochlorite dihydrate, the filtrate may be treated with lime to form basic calcium hypochlorite or used as bleach liquor.
U~S~ Patent No. 1,718,284, issued to Anthony George et al on June 25, 1929, describes a process in which lime and caustic soda are added to an eutectic solution of sodium chloride and calcium hypochlorite, the mixture i5 chlorinated and sodium chloride is quickly precipitated and separated from an unstable solution of calcium hypo-chlorite. Calcium hypochlorite dihydrate is then precip itated. In an alternate-embodiment, sodium hypochlorite and lime are chlorinatPd in an eutectic solution of sodium chloride and calcium hypochlorite with the ~odiu~ chloride and calcium hypochlorite dihydrate being precipitated and separated sequentially as de~cribed above.
.
C-6645 U.S. Patent No. 1,718,285, issued to Anthony George on June 25, 1929, discloses a process for chlorinating an aqueous slurry of lime in the presence of a solution of . sodium hypochlorite to form a slurry of calcium hypochlorite .
dihydrate. The slurry is evaporated to dryness to recover . calcium hypochlorite, or alternatively the calcium hypo- .:
chlorite is precipitated from a dilute NaCl solution, then separated and dri~d.
A process for calcium hypochlorite dihydrate manufacture is disclosed in U.S. Patent No. 3,572,989, issued to Seiji Tatara et al on Ma.rch 30, 1971, in which concentrated sodium hydroxide is added to an aqueou~ solution saturated with .
calcium hypochlorite and sodium chloride, and in a first step, the mixture is chlorinated and sodium chloride crystals are removed. In a second step, slaked lime and water are added to -the reaction mixture and the mixture is chlorinated. The resulting calcium hypochlorite dihydrate crystals are separated, and the mother liquor is recycled to the first step.
In all of the above processes the separation of calcium hypochlorite from sodium chloride takes place by either a) precipitating sodium chloride from a metastable solution of calcium hypochlorite where the separation must be carried out quickly to be effective, or b) precipitating calcium hypochlorite dihydrate from sodium chloride in solutions which must be very dilute to hold the ~odium chloride in solutionO
In both a) and b) above, there is a loss of product by co-precipitation or incomplete precipit:ation and in b) above there is the necessity to treat or dispose of large volumes of a dilute sodium chloride solution containing calcium hypochlorite values.
The process described in U.S. Patent No. 3,895,099, issued July 15, 1975, describes another process for preparing calcium hypochlorite wherein the filtrate, after removal of calcium hypochlorite dihydrate crystals is reacted with an alkali metal hydroxide to form a lime slurry, the lime is separated and recycled to the calcium hypochlorite reactor. Although this technique permits the recovery of calcium values which are normally lost in the previously defined calcium hypochlorite processes, one of the problems encountered is the difficulty in separating the line particles from the resulting lime slurry.
There is a need in the art at -the present time to improve the recovery of calcium values in calci~m hypochlorite processes and to improve the separation rate of lime from lime slurry formed in an effort to recover calcium values.
It is a primary object of this invention to provide an improved process for separating lime from lime slurry.
Another object of this invention is to provide an improved process for preparing calcium hypochlorite from lim~, alkali metal hydroxide and chlorine.
A further object of this invention is to provide:an improved process for preparing calcium hypochlorite wherein .
~ ~t~ ~ ~ 6 -6645 the proportion of impurities in waste streams is substantially reduced.
These and other objects of the invention are accomplished in a process for pxecipitating lime in a reaction of an alkali metal hydroxide with an aqueous solution of calcium hypochlorite to form a lime slurry, and separating the lime from the resulting slurry, utilizing an improvement which comprises maintaining a p~I in the range from about 11 to about 13O5 during said reaction, whereby hemi-basic calcium hypochlorite er~stals form in said lime slurry and aid in the separation of the lime from the slurry. In addition, washing of the lime particles to remove impurities is easily 0ffected because of the improved contact between wash liquor and lime particles and ease of separation of wash liquor from the lime particles that is effected by the presence of hemi-basic calcium hypachlorite crystals in the lime particles~
More in detail, any a~ueous solution containing calcium hypochlorite may be processed in accordance with the process of this invention. Filtrates processed in calcium hypochlorite processes af~er separation of the calcium hypochlorite product, are particularly useful as a starting material in the process of this invention.
Generally, these filtrates are aqueous solutions containing soluble calcium hypochlorite values as well as reaction by-products such as sodium chloride and sodium hypochlorite , or calcium chloride. A typical filtrate obtained i~ com-~5--~L~7~
C-6645 mercial calcium hypochlorite processes will have the following analyses:
Components Pe:rcent ~y Wei~ht ~road Range Narrow Range Calcium hypochlorite 5-12 9.5-10.5 Sodium hypochlorite 0-3.0 0-0.5 Sodium chloride 16-20 17-18 Calcium chloride 0-2 0-0.5 Water 68-75 69-73 While the above analysis is a typical analysis of a starting calcium hypochlorite solution, it will be recognized by those slcilled in the art that the composition of the calcium hypochlorite filtrate will depend upon the type of process employed in the preparation of calcium hypochlorite. For example, in some commercial processes, sodium chloride is separated as a solid before calcium hypochlorite is separated, and the resulting filtrate will contain substantially less sodium chloride. In other processes, no sodium components are employed and the main impurity is calcium chloride rather than sodium chloride. In the calcium systems, a typical filtrate may have the following analysis.
Com~onents Percent b~ ~eight Broad Range Narrow Range Calcium hypochlorite 1-10 1-8 Calcium chloride 15-40 18-35 Calcium hydroxide b .1 `1. o o . 4-o . 6 Water S0-85 60-80 ., ,.: .:
. - . - .
31 ~)7~6 C-6645 The bene~its of applicant's improved process are also applicable to such filtrates.
Any alkaline compound capable of precipitating calcium values as lime fxom the aqueous solution of calcium hypo-chlorite may be employed in this process. Typical examples of alkaline compounds are alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and mixtures thereof. However, other suitable alkaline hydroxides include barium hydroxide, cesium hydroxide, rubidium hydroxide and strontium hydroxide.
Sufficient alkaline hydroxide is added to the aqueous solution of calcium hypochlorite to adjust the pH to a range from about 11 to about 13.5, and preferably from about 12 to about 12.5. When sufficient alkaline hydroxide is added to adjust the pH of the calcium hypochlorite solution within the above ranges, a large portion of soluble calcium values is precipitated as lime. This may be accomplished batchwise or continuously, the latter technique being preferred. In addition, a portion of the lime and calcium hypochlorite values is co-precipitated as hemi-basic calcium hypochlorite crystals having the empirical formula:
Ca(OCl)2 1/2Ca(OH)~.
These hemi-basic crystals are substantially larger than the lime particles and range from about 2 to about 30 in microns in diameter~ In contrast, the lime particles have a size of less than about 2, and generally~ less than about 1 micron in diameter. The crystalline structure and particle size of the hemi-basic calcium hypochlorite crystals aid in the .
~7~6 C-6645 separation of the lime particles from the resulting slurry.
Filtration rates have been increased by a factor of from about 10 to 20 when compared wlth the filtration rate of lime slurries which do not contain the hemi-basic calcium hypochlorite crystals in accordance with the process of this invention. When the alkaline hydroxide is added to the aqueous calcium hypochlorite solution in a propoxtion sufficient to adjust the pH in excess of about 14, which is about 4 to about 5 percent excess alkali, the excess alkaline hydroxide decomposes the hemi-basic crystals and the filtration rate of the lime slurry decreases drastically.
If the proportion of alkaline compound added to the calcium hypochlorite solution is not enough to form a pH above about 11.0, decreased precipitation of the calcium values as lime occurs and a substantial content of calcium remains in the filtrate, resulting in substantial calcium values entering the sodium hypochlorite system.
In one embodiment of the invention, the alkaline hydroxide, generally as a 50 percent by weiyht aqueous solu-tion of sodium hydroxide, is added to a dilution tank in which a recycle stream of precipitated paste filtrate is used to dilute the sodium hydroxide to about 10 to 20 percent NaOH. This diluted sodium hdyroxide over~lows into a reactor where it reacts with the incoming paste filtrate containing calcium hypochlorite. With more concentrated NaOH
streams, the reaction is difficult to control and the filterability- varies widely. If water were used to dilute ~; the caustic to the 10 to 20 percent NaOH, too much water , ~ ~.
. ' ~
~a~7~
C-6645 would be added to the process requiring more evaporation in the chlorinator evaporator. For examp:Le, 50 percent sodium hydroxide has only 1 pound of water per pound of NaOH
as compared to 9 pounds of water per pound of NaOH at 10 percent caustic.
The reaction between the alkaline compound and the calcium hypochlorite solution is carried out at a temperature from about 10 to about 50 and preferably from about 27-32C. The reaction is generally carried out in a continuous reactor at atmospheric pressure, but slightly elevated or reduced pressure may be used, if desired.
The residence time in the reaction zone or a suitable storage zone prior to recovering or separating the mixture of lime and hemi-basic calcium hypochlorite from the reaction mass generally ranges from about 20 to about 180 minutes and preferably from about 25 to about 45 minutes. Extended storage periods of the reaction mass, particularly at high caustic concentrations, will adversely affect the filtration rate.
After the reaction is completed a suitable separation technique such as filtrati.on, centrifuging and the like is employed to separate the lime product and co-precipitated hemi-basic calcium hypochlorite crystals from the resulting slurryl When vacuum filters are employed, filtration rates from about ~0 to about 40 gallons per hour per square foot o filter surface are generally obtained. Washing of the filter cake to remove adhering liquid containing im-purities is easily effected because o the improved fil-tration rate imparted by the hemi-basic calcium hypochlorite particles.
_g_ .
The washed filter cake is generally comprised of the following components.
Components Percent by Weight Broad Range Narrow Range : Calcium hypochlorite 0.5-8 1-3 Calcium hydroxide (Total25-40 30-34 Sodium Hypochlorite 0.1-2.5 0.4-0.8 Sodium chloride 0.2-2.0 0.5-1.0 Water 50-75 60-70 :.
Calcium hypochlorite -hemi-basic 0.5-10.0 1-4 Free Lime 25-35 28-34 It can be seen from the above analysis that, the weight .ratio of lime to the crystalline hemi-basic calcium hypochlorite in the filter cake generally ranges from about
A variety of processes and modifications are known in the art for manufacturing calcium hypochlorite.
U.S. Patent No. 1,713,669, issued to Rob rt B.
MacMullin et al on May 21, 1929, discloses a process in which an aqueous slurry of lime is chlorinated, solid impurities are removed, and caustic and chlorine are added to produce calcium hypochlorite and alkali chloride.
The concentration of the calcium hypochlorite-alkali chloride mixture is kept dilute so that the alkali chloride remains in solution while the calcium hypochlorite dihydrate is precipitated. After separation of the solid calcium hypochlorite dihydrate, the filtrate may be treated with lime to form basic calcium hypochlorite or used as bleach liquor.
U~S~ Patent No. 1,718,284, issued to Anthony George et al on June 25, 1929, describes a process in which lime and caustic soda are added to an eutectic solution of sodium chloride and calcium hypochlorite, the mixture i5 chlorinated and sodium chloride is quickly precipitated and separated from an unstable solution of calcium hypo-chlorite. Calcium hypochlorite dihydrate is then precip itated. In an alternate-embodiment, sodium hypochlorite and lime are chlorinatPd in an eutectic solution of sodium chloride and calcium hypochlorite with the ~odiu~ chloride and calcium hypochlorite dihydrate being precipitated and separated sequentially as de~cribed above.
.
C-6645 U.S. Patent No. 1,718,285, issued to Anthony George on June 25, 1929, discloses a process for chlorinating an aqueous slurry of lime in the presence of a solution of . sodium hypochlorite to form a slurry of calcium hypochlorite .
dihydrate. The slurry is evaporated to dryness to recover . calcium hypochlorite, or alternatively the calcium hypo- .:
chlorite is precipitated from a dilute NaCl solution, then separated and dri~d.
A process for calcium hypochlorite dihydrate manufacture is disclosed in U.S. Patent No. 3,572,989, issued to Seiji Tatara et al on Ma.rch 30, 1971, in which concentrated sodium hydroxide is added to an aqueou~ solution saturated with .
calcium hypochlorite and sodium chloride, and in a first step, the mixture is chlorinated and sodium chloride crystals are removed. In a second step, slaked lime and water are added to -the reaction mixture and the mixture is chlorinated. The resulting calcium hypochlorite dihydrate crystals are separated, and the mother liquor is recycled to the first step.
In all of the above processes the separation of calcium hypochlorite from sodium chloride takes place by either a) precipitating sodium chloride from a metastable solution of calcium hypochlorite where the separation must be carried out quickly to be effective, or b) precipitating calcium hypochlorite dihydrate from sodium chloride in solutions which must be very dilute to hold the ~odium chloride in solutionO
In both a) and b) above, there is a loss of product by co-precipitation or incomplete precipit:ation and in b) above there is the necessity to treat or dispose of large volumes of a dilute sodium chloride solution containing calcium hypochlorite values.
The process described in U.S. Patent No. 3,895,099, issued July 15, 1975, describes another process for preparing calcium hypochlorite wherein the filtrate, after removal of calcium hypochlorite dihydrate crystals is reacted with an alkali metal hydroxide to form a lime slurry, the lime is separated and recycled to the calcium hypochlorite reactor. Although this technique permits the recovery of calcium values which are normally lost in the previously defined calcium hypochlorite processes, one of the problems encountered is the difficulty in separating the line particles from the resulting lime slurry.
There is a need in the art at -the present time to improve the recovery of calcium values in calci~m hypochlorite processes and to improve the separation rate of lime from lime slurry formed in an effort to recover calcium values.
It is a primary object of this invention to provide an improved process for separating lime from lime slurry.
Another object of this invention is to provide an improved process for preparing calcium hypochlorite from lim~, alkali metal hydroxide and chlorine.
A further object of this invention is to provide:an improved process for preparing calcium hypochlorite wherein .
~ ~t~ ~ ~ 6 -6645 the proportion of impurities in waste streams is substantially reduced.
These and other objects of the invention are accomplished in a process for pxecipitating lime in a reaction of an alkali metal hydroxide with an aqueous solution of calcium hypochlorite to form a lime slurry, and separating the lime from the resulting slurry, utilizing an improvement which comprises maintaining a p~I in the range from about 11 to about 13O5 during said reaction, whereby hemi-basic calcium hypochlorite er~stals form in said lime slurry and aid in the separation of the lime from the slurry. In addition, washing of the lime particles to remove impurities is easily 0ffected because of the improved contact between wash liquor and lime particles and ease of separation of wash liquor from the lime particles that is effected by the presence of hemi-basic calcium hypachlorite crystals in the lime particles~
More in detail, any a~ueous solution containing calcium hypochlorite may be processed in accordance with the process of this invention. Filtrates processed in calcium hypochlorite processes af~er separation of the calcium hypochlorite product, are particularly useful as a starting material in the process of this invention.
Generally, these filtrates are aqueous solutions containing soluble calcium hypochlorite values as well as reaction by-products such as sodium chloride and sodium hypochlorite , or calcium chloride. A typical filtrate obtained i~ com-~5--~L~7~
C-6645 mercial calcium hypochlorite processes will have the following analyses:
Components Pe:rcent ~y Wei~ht ~road Range Narrow Range Calcium hypochlorite 5-12 9.5-10.5 Sodium hypochlorite 0-3.0 0-0.5 Sodium chloride 16-20 17-18 Calcium chloride 0-2 0-0.5 Water 68-75 69-73 While the above analysis is a typical analysis of a starting calcium hypochlorite solution, it will be recognized by those slcilled in the art that the composition of the calcium hypochlorite filtrate will depend upon the type of process employed in the preparation of calcium hypochlorite. For example, in some commercial processes, sodium chloride is separated as a solid before calcium hypochlorite is separated, and the resulting filtrate will contain substantially less sodium chloride. In other processes, no sodium components are employed and the main impurity is calcium chloride rather than sodium chloride. In the calcium systems, a typical filtrate may have the following analysis.
Com~onents Percent b~ ~eight Broad Range Narrow Range Calcium hypochlorite 1-10 1-8 Calcium chloride 15-40 18-35 Calcium hydroxide b .1 `1. o o . 4-o . 6 Water S0-85 60-80 ., ,.: .:
. - . - .
31 ~)7~6 C-6645 The bene~its of applicant's improved process are also applicable to such filtrates.
Any alkaline compound capable of precipitating calcium values as lime fxom the aqueous solution of calcium hypo-chlorite may be employed in this process. Typical examples of alkaline compounds are alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and mixtures thereof. However, other suitable alkaline hydroxides include barium hydroxide, cesium hydroxide, rubidium hydroxide and strontium hydroxide.
Sufficient alkaline hydroxide is added to the aqueous solution of calcium hypochlorite to adjust the pH to a range from about 11 to about 13.5, and preferably from about 12 to about 12.5. When sufficient alkaline hydroxide is added to adjust the pH of the calcium hypochlorite solution within the above ranges, a large portion of soluble calcium values is precipitated as lime. This may be accomplished batchwise or continuously, the latter technique being preferred. In addition, a portion of the lime and calcium hypochlorite values is co-precipitated as hemi-basic calcium hypochlorite crystals having the empirical formula:
Ca(OCl)2 1/2Ca(OH)~.
These hemi-basic crystals are substantially larger than the lime particles and range from about 2 to about 30 in microns in diameter~ In contrast, the lime particles have a size of less than about 2, and generally~ less than about 1 micron in diameter. The crystalline structure and particle size of the hemi-basic calcium hypochlorite crystals aid in the .
~7~6 C-6645 separation of the lime particles from the resulting slurry.
Filtration rates have been increased by a factor of from about 10 to 20 when compared wlth the filtration rate of lime slurries which do not contain the hemi-basic calcium hypochlorite crystals in accordance with the process of this invention. When the alkaline hydroxide is added to the aqueous calcium hypochlorite solution in a propoxtion sufficient to adjust the pH in excess of about 14, which is about 4 to about 5 percent excess alkali, the excess alkaline hydroxide decomposes the hemi-basic crystals and the filtration rate of the lime slurry decreases drastically.
If the proportion of alkaline compound added to the calcium hypochlorite solution is not enough to form a pH above about 11.0, decreased precipitation of the calcium values as lime occurs and a substantial content of calcium remains in the filtrate, resulting in substantial calcium values entering the sodium hypochlorite system.
In one embodiment of the invention, the alkaline hydroxide, generally as a 50 percent by weiyht aqueous solu-tion of sodium hydroxide, is added to a dilution tank in which a recycle stream of precipitated paste filtrate is used to dilute the sodium hydroxide to about 10 to 20 percent NaOH. This diluted sodium hdyroxide over~lows into a reactor where it reacts with the incoming paste filtrate containing calcium hypochlorite. With more concentrated NaOH
streams, the reaction is difficult to control and the filterability- varies widely. If water were used to dilute ~; the caustic to the 10 to 20 percent NaOH, too much water , ~ ~.
. ' ~
~a~7~
C-6645 would be added to the process requiring more evaporation in the chlorinator evaporator. For examp:Le, 50 percent sodium hydroxide has only 1 pound of water per pound of NaOH
as compared to 9 pounds of water per pound of NaOH at 10 percent caustic.
The reaction between the alkaline compound and the calcium hypochlorite solution is carried out at a temperature from about 10 to about 50 and preferably from about 27-32C. The reaction is generally carried out in a continuous reactor at atmospheric pressure, but slightly elevated or reduced pressure may be used, if desired.
The residence time in the reaction zone or a suitable storage zone prior to recovering or separating the mixture of lime and hemi-basic calcium hypochlorite from the reaction mass generally ranges from about 20 to about 180 minutes and preferably from about 25 to about 45 minutes. Extended storage periods of the reaction mass, particularly at high caustic concentrations, will adversely affect the filtration rate.
After the reaction is completed a suitable separation technique such as filtrati.on, centrifuging and the like is employed to separate the lime product and co-precipitated hemi-basic calcium hypochlorite crystals from the resulting slurryl When vacuum filters are employed, filtration rates from about ~0 to about 40 gallons per hour per square foot o filter surface are generally obtained. Washing of the filter cake to remove adhering liquid containing im-purities is easily effected because o the improved fil-tration rate imparted by the hemi-basic calcium hypochlorite particles.
_g_ .
The washed filter cake is generally comprised of the following components.
Components Percent by Weight Broad Range Narrow Range : Calcium hypochlorite 0.5-8 1-3 Calcium hydroxide (Total25-40 30-34 Sodium Hypochlorite 0.1-2.5 0.4-0.8 Sodium chloride 0.2-2.0 0.5-1.0 Water 50-75 60-70 :.
Calcium hypochlorite -hemi-basic 0.5-10.0 1-4 Free Lime 25-35 28-34 It can be seen from the above analysis that, the weight .ratio of lime to the crystalline hemi-basic calcium hypochlorite in the filter cake generally ranges from about
2.5:1 to about 50:1 and preferably from about 7:1 to about ,~
30:1.
The liquid recovered after separation of the lime from -. the slurry generally contains the following components in the following proportions.
: .:
.. ' .:
: ', ' --10-- ..
:. ...
, .. . . ~ . .
:. .. . .
C-6645 Components Percent by Weight Broad Ran~eNarrow Range Calcium hypochlorite 0~2~0 0-0.1 Calcium hydroxide 0.01-1.0 0.02-0.0S
Sodium hypochlorite 8.50 12.09.5-10.0 Sodium chloride 15O0-18 16.5-17.0 Water 70-77 72-75 NaOH 0-1.0 0.1-0.4 pH 11-13.512.1-12.5 The wet lime cake, particularly if produced in a contin-uous calcium hypochlorite process, can be recycled to the mixing zone and then the slurry chlorinator. Because of the washing, there is substantially no recycle of sodium chloride and other impurities in the lime, thereby reducing the size of recycle streams and improving the yield of calcium hypochlorite based upon initial limP fed to the reaction.
The liquid recovered after separation of the lime can be further processed to recover salt values by evaporation, caustic addition, and chlorination. It may also be used in the preparation of a bleach solution.
....
~7~
As indicated above, the technique for recovering lime from aqueous solutions of calcium hypochlorite in accordance with this invention can be applied to virtually any known process for preparing calcium hypochlorite where calcium values are lost af-ter separation of the calcium hypochlorite dihydrate crystals. The novel process of this invention in particularly suitable for use in the process for preparing calcium hypochlorite described in U.S. Patent No.
30:1.
The liquid recovered after separation of the lime from -. the slurry generally contains the following components in the following proportions.
: .:
.. ' .:
: ', ' --10-- ..
:. ...
, .. . . ~ . .
:. .. . .
C-6645 Components Percent by Weight Broad Ran~eNarrow Range Calcium hypochlorite 0~2~0 0-0.1 Calcium hydroxide 0.01-1.0 0.02-0.0S
Sodium hypochlorite 8.50 12.09.5-10.0 Sodium chloride 15O0-18 16.5-17.0 Water 70-77 72-75 NaOH 0-1.0 0.1-0.4 pH 11-13.512.1-12.5 The wet lime cake, particularly if produced in a contin-uous calcium hypochlorite process, can be recycled to the mixing zone and then the slurry chlorinator. Because of the washing, there is substantially no recycle of sodium chloride and other impurities in the lime, thereby reducing the size of recycle streams and improving the yield of calcium hypochlorite based upon initial limP fed to the reaction.
The liquid recovered after separation of the lime can be further processed to recover salt values by evaporation, caustic addition, and chlorination. It may also be used in the preparation of a bleach solution.
....
~7~
As indicated above, the technique for recovering lime from aqueous solutions of calcium hypochlorite in accordance with this invention can be applied to virtually any known process for preparing calcium hypochlorite where calcium values are lost af-ter separation of the calcium hypochlorite dihydrate crystals. The novel process of this invention in particularly suitable for use in the process for preparing calcium hypochlorite described in U.S. Patent No.
3,895,099, issued July 15, 1975.
Figure 1 is a flow sheet of a preferred embo~iment of the present invention showing the separation of calcium hypochlorite and precipitation of lime from the paste liquor.
More in detail, in the process of Figure 1, lime (both fresh lime and recycle lime of the type described more fully below), water and sodium hypochlorite are admixed in mixing `~ zone 1 to form a mixing zone slurry~ Mixing zone 1 is a mixing tank or other suitable container with agitation means for blending the various components fed thereto. There may be some degree of reaction between the various components fed to mixing zone 1, but an important function of mixing zone 1 is to admix the components, and therefore it is referred to as a "mixing zone", even though some "reaction" may occur in some embodiments of the inventionO
The resulting mixing zone slurry is conveyed to slurry chlorinator 2 and reacted with chlorine. Slurry chlorinator 2 is any suitable chlorination apparatus provided with ' , ~ . : . ~, 1~7~(1336 C-6645 agitation means for maximum contact ~etween chlorine and slurry. It is preferred to employ as slurry chlorinator 2 an evaporator chlorinator which utilize~ the chlorination technique described in U.S. Patent No. 3,241,912, issued to Bernard H. Nicolaisen on March 22, 1966. Tempera~ure within slurry chlorinator 2 is main~ai.ned within the range from about 0 to about 50 and preferably from about 20 to about 32C.
During chlorination of the slurry in slurry chlori-nator ~, lime reacts with chlorine to form calcium hypo-chlorite in accordance with Equation (1):
tl) Ca(OH)2 ~ ~12 ~ 1/2 Ca(ClO)2 + H2O ~ 1/2 CaC12 Some sodium hydroxide may be present in the mixing zone slurry as a result of feeding sodium hydroxide ~not shown) to mixing ~one 1, or it may be present in the recycle lime fed to a mixing zone 1. Any sodium hydroxide :
present in the sluxry chlorinator 2 ic reacted with chlorine to form sodium hypochlorite in accordance with ; Equation (2):
(2) 2NaOH ~ C12 ~ NaClO ~- NaCl + H2O
Sodium hypochlorite present in slurry chlorinator 2 reacts with calcium chloride to form sodium chloride and additional calcium hypochlorite in accordance with Equation (3):
: (3) NaClO ~ 1/2 CaC12 ~ 1/2 Ca(ClO)2 ~ NaCl :~ -13-.. . . . .
C-6645 The primary products of slurry chlorinator 2 are calcium hypochlorite, sodium chloride and water. At start-up of the process, it is preferred, but not necessary to fill slurry chlorinator 2 with a sluxry or "paste" of calcium hypochlorite solids suspended in an aqueous solution of sodium chloride and calcium hypochlorite, with an excess alkali concentration in the slurry being less than about 1.0 and pre~erably less than about 0.50 percent by weight. The rate of feed of mixing zone slurry and chlorine to slurry chlorinator 2 and rate of evaporation of water, if any, are adjusted to maintain the concentxation of unreacted alkali during the reaction below about 1.0 percent. Continuous chlorination of the slurry in this manner causes the formation of coarse calcium hypochlorite dihydrate crystals which are : much more easily separated fxom paste liquor in cake separator 3, than are calcium hypochlorite dihydrate crystals prepared in a conventional triple salt process or a batch type process.
A portion of the resulting "paste" comprised of solid ! calcium hypochlorite dihydrate and a "paste" liquor, which is predominately an aqueous solution of sodium chloride and calcium hypochlorite is continuously withdrawn from slurry chlorinator 2 and conveyed to cake separator 3.
Cake separator 3 is a filter, centrifuge, or other suitable solid-liquid separating apparatus capable of separating a moist cake of calcium hypochlorite dihydrate crystals from the aqueous solution o sodium chloride and calcium hypochlorite.
~L~)7~ 6 C 6645 Moist cake from cake separator 3 generally contains from about 40 to about 6C percent by weight of calcium hypochlorite dihydrate, from about 2 to about 15 percent by weight of sodi~n chloride, and from about 38 to about 52 percent by weight of water. Moist cake is generally conveyed to dryer 4 where it is heated to remove most of the water. Dryer 4 is any suitable drying unit or unit~
capable of reducing the moisture content of the oalcium hypochlorite caXe to the desired level without causing excess decomposition of the calcium hypochlorite particles.
Generally the water content of the calcium hypochlorite is reduced in dryer 4 to below about 10 percent by weight and preferably from about 0.5 to about 7.5 percent by weight. The calcium hypochlorite content of the dried calcium hypochlorite generally ranges from about 65 to about 85, and preferably from about 70 to about 80 percent by weight. The remainder of the dried calcium hypochlorite is predominately sodium chloride. The dried product is then placed in suitable containers, with or without prior size classification or other processing such as pelletizing, prior to use in water treatment or other utility.
"Paste liquox'l (or "paste filtrate" when cake separator 3 is a filter) is an aqueous sodium chloride solution from cake separator 3 which also contains soluble calcium hypochlorite. This paste liquor is conveyed to caustic reactor 5, which is any suitable mixing tank reactor provided wi~h agitation means, where it is reacted with an aqueous solution of a soluble metal hydroxide, preferably sodium hydroxide, to form a lime slurryO
~15-~7~3~i C-6645 The aqueous solution of sodium hydroxide is prepared by admixing sodium hydroxide or other alkaline compounds in dilution tank 6 with a portion of the lime slurry from caustic reactor 5. The lime slurry is conveyed from caustic reactor 5 to dilution tank 6 by means of caustic reactor pump 7. SUfficient lime slurry is recycled to the ; dilution tank to form an alkaline aqueous slurry in which the proportion of sodium hydroxide or other soluble metal hydroxide is in the range from about 10 -to ahout 20 percent by weight.
; The recycle flow of lime slurry is preferably maintained uniform, and as the reaction requires more or less alkali to maintain the desired pH in reactor 5, the control system adds more or less caustic to the dilution tank resulting in a variation of the NaOH concentration in the dilution system.
The slurry in the caustic reactor 5 is maintained at a pH of about 11.0 to about 13.5~ and preferably from about 12 to 12.5 by incxeasing or decreasing the caustic flow to dilution tank 6.
A portion of the lime slurry is conveyed to lime separator 8 such as a filter, where the solid lime particles and the resulting hemi-basic calcium hypochlorite crystals are separated from the aqueous mother liquor, which pre-dominates in sodium chloride.
The reaction between the alkaline compound such as sodium hydroxide and the calcium hypochlorite in the paste liquor proceeds in accordance with Equations (4) and (5).
. . , , , : .
, . . . . , ,: ... .
1~'7~
C-6645 (4) 2NaOH + Ca(ClO)2 -- ~ Ca(OH)2 ~ 2NaClO
(5) 1/2 Ca(OH)2 ~ Ca(OCl)2 ) Ca(OCl)2 1/2 Ca (~)2 The crystals of lime and hemi-basic calcium hypo-chlorite crystals in the cake formed i:n lime separator 8 are easily washed with water to remove excessive salt from the lime cake and the washed cake is recycled to mixing zone 1.
Mother liquor, the aqueous solution of sodium chloride and sodium hypochlorite recovered in lime separator 8, may be utilized as bleach liquor. This mother liquor contains essentially no calcium hypochlorite values. Therefore, a much larger percentage of lime fed into the system is recovered as large crystals Qf calcium hypochlorite dihydrate rather than as an impurity in an effiuent stream or sold as a less expensive bleach liquor. However, mother liquor from lime separator 8 is preferably recycled to ~he proces~ as described more fully below.
In a second embodiment of the invention an aqueous solution of sodium chloride and sodium hypochlorite from lime separator 8 i9 conveyed to an evaporator-chlorinator ~not shown~ where the aqueous solution is concentrated by evaporation and is reacted with sodium hydroxide and chlorine to form a slurry of solid sodium chlorlde in an aqueous solution of sodium hypochlorite.
8~
C-6645 This evaporation and reaction is carried out in any suitable evaporation apparatus and chlorinator-reactor provided with agitation means. Simultaneous evaporation and chlorination may be carried out in an evaporative chlorinator using the chlorination technique described in U.S. Patent No. 3,241,912, issued to Bernard H. Nicolaisen on March 22, 1966.
: In a preferred embodiment of the invention, the mother liquor is first concentrated.by evaporation with steam, in an evaporator (not shown) and the resulting con-centrated mother liquor is then reacted with chlorine and sodium hydroxide in the evaporator-chlorinator, utilizing the heat of chlorination to complete evaporation of the mother liquor and effect precipitation of salt in the mother liquor.
Evaporation prior to reaction in the evaporator-chlorinator is generally more economical since the rate of evaporation of water is more rapid from the dilute mo~her liquor prior to reacting and therefore smaller, less expensive evaporatoxs may be used than are required ~or the more concentrated slurry of salt and mother liquorO .~:
In another embodiment o~ the invention~ no chlorine .
or sodium hydroxide are added to the evapora~or-chlorinator and only evaporation takes place in the evaporator-chlorinator to effect precipitation of salt in the mother liquor. The degree of evaporation will depend upon the .
initial mother liquor concentration, C-6645 When chlorination is used, the temperature during chlorination is generally maintained within the range from about 0 to a~out 50 and preferably from about 20 to about 32C.
In this embodiment, sufficient chlorine and sodium hydroxide are added to and sufficient water is removed from the mother liquor fed to the evaporator-chlorinator to maintain in the solution portion of the resulting slurry a sodium hypochlorite concentration within the range from about 15 to about 40 and preferably from about 25 to about 35 percent by weight. In addition, the soluble soclium chloride concentration in the solution portion of the slurry from evaporator-chlorinator is maintained from about 4 to about 14 and preferably from about 4.8 to about 7.7 percent be weight. The solid sodium chloride concentration in '' the slurry from the evaporator~chlorinatox ranges from a~out 15 to about 35, and preerably rom about 18 to about 28 percent by weight. The resulting slurry i9 conveyed to a , salt separator (not shown) which is a suitable filker, centrifuge or similar solid-liquid separating apparatus.
In the salt separator, relatively pure sodium chloride crystals are separated from the aqueous sodium hypochlorite solution. These crystals may be used in the preparation of br,ine which is used as a feed material for electrolytic cells used in the preparation of chlorine and sodium hydroxide.
~19-C-66~5 The aqueous solution of sodium h~pochlorite which is also separated from the salt separator~ is recycled to mixing zone 1 for further admixing with fresh lime and recylced lime.
This embodiment of the invention not only results in easily filtexable lime, large crystals of hemi-basic calcium hypochlorite and more efficient utilization of calcium values as calcium hypochlorite, as in the embodiment of Figure 1, but also produces relatively pure sodium chloride in solid form, which has utility in the preparation of brine feed for electrolytic cells. There are no impure aqueous solutions of sodium chloride, calcium hypochlorite or the like which need to be disposed of in the latter embodiment thereby avoiding a seriou~ pollution pro~lem.
A third em~odiment of the invention includes the second embodiment above as well as a technique for purifying at least a portion of the fresh lime fed to the p~ocess prio~ to admixing with sodium hypochlorite in mixing zone 1 and recycling at least a portion of the paste liquor to mixing zone 1.
1Ci7q;~
C-6645 In the third embodiment, an aqueous slurry of fresh lime is chlorinated in lime chlorinator (not shown) to form an aqueous solution of calcium hypochlorite and calcium chloxide in accordance with Equation (1). Impurities in the fresh lime include insoluble impurities such as silica, aluminum salts, iron salts, magnesium ~alts, magnesia, unburned limèstone (calcium carbonate and magnesium caxbonate) and other compounds in ~race quantities. The~e impurities present in the fresh lime remain insoluble in the aqueous solution formed in the lime chlorinator and form a slurry with the.aqueous solution of calcium hypo-chlorite and ~alcium chloride. This slurry is conveyed to an impurity separator (not shown), which is a suitable solid-liquid separator such as a filter, centrifuge or the like, where solid impurities are separatedO Solid impurities ~rom the impurity separator are generally disposed of as solid waste, land fill or the like. The aqueous solution of calcium hypochlorite and calcium chloride from the impurity separator is conveyed to mixing zone 1. As indicatPd above, the primary function of mixing zone 1 is to ef~ect admixing of the components fed thereto. However, in the third embodiment~ the calcium chloride component of the aqueous solution from the impurity separator is reacted in mixing zone 1 with sodium hypochlorite to ~orm an aqueous : .
.
~70~)8~i C-6645 solution of calcium h~pochlorite and sodium chloride in accordance with Equation t3~.
In the third emhodiment, at least a portion of the fresh lLme is purified in the lime chls)rinator and impurity separator prior to feeding to mixing zone 1, and a portion of the fresh lime fed to mixing zone 1 may be untreated.
The ratio of fresh lime in each of these feed streams depends upon the initial purity and activity of the fresh lime fed to the process as well as specifications for " 10 impurities required for the calcium hypochlorite productO
Thus, if the fresh lime i5 relatively pure and the ~tandards for purity of the calcium hypochlorite are not high, then little or no fresh lime has to be purified prior to feeding to mixing zone 1. However, if the lime is relatively impure, then a large fraction or all of the ~resh lime is ~ :
purified in the lime chlorinator and impurity separator prior to feeding to mixing zone 1.
In all of the above defined embodiments, in order to maintain within the mixing zone slurry the concentration of lime (both fresh lime, if added, and recycled lime) within the desired range, and the concentration of sodium hypochlorite within the desired range, additional sodium hydroxide may be added to mixing zone 1. In addition, in order to improve control of the chlorination and heat transfer in slurry chlorinator 2 a portion of the paste liquor from cake separator 3 may be recycled to mixing zone 1.
, C-6645 The primary raw materials for the pro~e~s of this invention are lime, sodium hydroxide, chlorine cmd water.
Fresh lime is added to the process at mixing zone 1 and~or the lime chlorinator. One of the advantages of a preferred embodiment of this invention is that relatively impure lime may be utilized to prepare a relatively pure calcium hypochlorite product. For example, lime having an active lime content as low as 85 percent by weight or less may be added to the lime chlorinator in accordance with the third embodiment of this invention, and procluce a relatively pure calcium hypochlorite product. Generally the active lime content of the lime fed to the lime chlorinator and/or mixing zone 1 ranges from about 85 to about 100 percent, and preferably from about 90 to about 97 p rcent by weight of active lime. Lime impurities of the type described above may range from about n to about 15 percent and generally from about 3 to about 10 percent by weight of the lime.
Typical illustrative specifications for a preferred ~ -fresh lime feed and for an acceptable lime feed are as follows:
Component Preferred Acceptable C~(OH)2 min.% g5.0 85 CaCO3 max.~ 1.0 3.0 MyO max.% 0.5 3~5 SiO~ max.~ 0.5 2.5 Fe2O3~A12O3 max.~ 0.5 1.5 CaSO4 max.~ 0.5 1.5 -2~-. . , . . :
v~
C-6645 Generally from 0 to less than about 1~2 of the lime feed ; meeting the above-illustrative preferxed specifications does not need to be processed in accordance with the lime purification embodiment of the third embodiment. However, when processing lime feed meeting the above illustrative acceptable specifications a major portion up to all of the feed may have to be processed in accordance with the lime purification step of the third embodiment. The average particle size of fresh lime added to the process generally is substantially all -325 mesh (wet screen analy~is) but particles up to about ~~00 mesh may be employed if desired.
When the impurity content of lime in the lime feed is greater than about S percent by weight, it may be desirable to add the lime chlorinator a carbonating agent such as carbon dioxide or sodium carbonate to enhance precipita-tion and removal of the impurities in solid form from impurity separator 10.
As indicated above, fresh lime is fed to the system either through the lime chlorinator or mixing zone 1, or a combination of both. It is preferred to feed-from about 25 to about 100 percent of the fresh lime into the lim~ chlorinator and any balance of fresh lime being fed into mixing zone 1. When all of the fre~h lime is fed to the lime chlorinator then substantially all of the lime fed to mixing zone 1 is in the form of recycle lime slurry, the concentrated slurry of precipitated lime.
Fresh lime is fed to the lime chlorinator as an aqueous slurry containing from about 10 to about 30 percent, and C~6645 preferably ~rom about 15 to about 20 percent by weight of active lime. Into mixing zone 1, lime may be added dry or as a slurry up to about 50 percent lime by weight, Lime added to mixing zone 1 as recycle lime rom lime separator 8 is substantially pure lime~ having an active lime content of from about 85 to about 100 percent by weight. The solid content of the recycle lime slurry generally ranges from about 20 to about 50 and preferably from about 25 to about 35 percent by weight of solids, which are predominately lime, and containing some hemi-basic cryskals of calcium hypochlorite.
Sodium hydroxide is added to dilution tank 6, the evaporator chlorinator and if desired, to mixing zone 1, as a concentrated aqueous solution, generally ranging from about 40 to about 60 percent by weight of sodium hydroxide. However, sodium hydroxide may be added in anhydrous form to dilution tank 6 and the evaporator-chlorinator, and if desired, to mixing zone 1.
In addition, sodium hypochlorite added to mixing ~one 1 in Figure 1 may be prep~red by chlorinating an a~ueous solution of sodium hydroxide, in a suitable agitated chlorinator reactor (not shown). The sodium hydroxide concentration in the aqueous solution used to make sodium hypochlorite for feed to mixing zone 1 of Figure 1 ranges from about 20 to about 75 and preferably fromabout 35 to about 5S percent by weight. In the second and third embodiments, sodium hypochlorite solution is added to the mixing zone as a recycle stream from the ~alt separator. Concen~ration of this recycle stream by ~2~-. .
~7~
.
C-6645 evapoxation in the evaporator-chlorinator is generally sufficient to maintain the desired sodium hypochlorite concentration in mixing zone l. However, if desired, any necessary additional sodium hydroxide may be added dire¢tly to mixing zone 1 or additional sodium hypo-chlorite may be prepared by chlorinating an aqueous solution of sodium hydroxide and then addad to mixing zone 1 as described above with respect to Figure 1, or may be added to mother liquor prior to or simultaneous with chlorination in the evaporator-chlorinator.
The overall reaction for the process of this invention may be illustrated by Equation ~6):
~6) Ca(OH)2 + 2C12 + 2NaOH ~ Ca~ClO)2 ~ 2NaC1 ~ 2H2O
Thus, the stoichiometric proportion of fresh sodium hydroxide fed to the process is equivalent to two moles of sodium hydroxide per mole of active lime present in the fresh lime fed to the process. As indicated in the embodiment of Figure 1, sodium hydroxide is fed to caustic reactor 5 and may be used to form sodium hypochlorite fed to mixing zone 1. In the second embodiment, sodium hydroxide is added to caustic reactor S and the evaporator-chlorinator (not shown).
In the third embodiment, sodium hydroxide is added to caustic reactor 5, and to either the evaporator-chlorinator or mixing zone 1, or both. The relative ratio of proportions of sodium hydroxide added to the di~ferent units of the di~ferent embodimen~s may be varied over a wide range.
Generally, above about 20 and preferably ~rom about 22 to `
.
0~8~
C-6645 about 35 percent o~ the stoichiometric proportion of sodium hydroxide required in Equation (6~ is added to caustic reactor 5 to precipitate lime and hemi~basic calcium hypo-chlorite crystals from the paste liquor. The balance of the stoichiometric proportion of sodium hydroxide is added in the embodiment of Figure 1 as sodium hypochlorite to mixing zone 1. The balance of sodium hydroxide is added to the evaporator-chlorinator in the second embodiment.
The balance o sodium hydroxide is added either entirely to evaporator-chlorinator in the thixd embodiment, or up to about 70 percent of the balance of the stoichio-metric proportion may be added to mixing zone 1.
In the embodiment of Figure 1 and the second embodi-ment where lime ~both fresh and recycled) and sodiwm hypochlorite solution are added to mixing zone 1, the resulting mixing zone slurry has a lime concentration ranging from about 1 to about 25 and preferably from about 2 to about 20 weight percent and a sodlum hypochlorite concentration ranging from about 1.5 to about 30, and : 20 preferably from about 2 to about 26 percent by weight. In the third embodiment, when all or part of the fresh lime is purified in the lime chlorinator and impurity separator to form an aqueous solution of calcium hypochlorite and calcium chloride which is fed to mixing zone 1~ the resulting mixing zone slurry has a lime concentration and sodium hypochlorite concentration within the above ranges as well as a concentration of calcium hypochlorite ranging from a~out 0 to about 30, and preferably from about 5 to about 26 percent by weight. All of the calcium chloride fed to .
~C~7~
C-6645 mixing zone 1 re~cts with sodium hypochlorite to form calcium hypochlorite and sodium chloride in acco.rdance with Equation (3).
The ultimate water content in the mixing zone slurry is controlled by adjusting the water content of the various feed streams to mixing zone 1. For example, the water content of the aqueous solution of calcium hypochlorite and calcium chloride (when lime purification of the third embodiment is used), the water content of any lime slurry added, ~either fxesh or recycled lime) the water content of the sodium hypochlorite (either fresh sodium hypo-chlorite or recycled), and.if desired, the quantity of re-cycled paste liquor from cake separator 3 are controlled to obtain a mixing zone slurry of the desired concentration range described above.
.As indicated above, slurry-chlorinator 2 at start-up, is preferably filled, but not necessarily filled, with a slurry of calcium hypochlorite solids suspended in an aqueous solution of sodium chloride. The excess lime or other alkali in the slurxy is maintained below about 1.0 and preferably less than about 0.5 percent by weight of the sluxry. The feed xate of mixing zone slurry and chlorine to mixing slurry chlorinator 2 and the withdrawal rate of the resulting calcium hypochlorite paste are adjusted to achieve substantially complete chlorination of the calcium hydroxide values fed to slurry chlorinator 2 in mixing zone slurry, while maintaining the free lime or alkali conce.ntration in slurry chlorinator 2 preferably below about 1.0 percent by weight of the slurry.
~7(~
C-6645 Chlorine is added to slurry chlorinator 2 as well as the evaporator-chlorinator and lime chlorinator in either gaseous or liquid form. The chlorination reactions are carried out preferably continuously in an evaporator type chlorinator of the type described above.
Paske from slurry chlorinator 2 is predominately a slurry of calcium hypochlorite dihydrate in an aqueous solution of sodium chloride and calcillm hypochlorite~ The paste contains calcium hypochlorite dihydrate crystals in the concentration of from about 10 to about 35 and preferably from about 15 to about 30 percent by weight. These crystals are predominately rectangular platelets which are several microns in thickness, and have substantially equal sides ranging from about 50 to about 300 microns in length with the major portion haviny sides ranginy from about 100 microns to about 250 microns in length. Generally, less than about 5 percent of the crystals are "twin crystals"
which entrain paste liquor, which are difficult to separate from the paste liquor, ancl which are difficult to dry.
Since more than about 95 percent of the calcium hypochlorite dihydrate crystals obtained by the process of this invention may be large platelets or cohesive agglomerates, there is a minimal amount of paste liquor entrained in the crystals during the separation in cake separator 3, even when filtered on a drum filter. The crystals are easier to separate from the paste liquor in cake separator 3 and are easier to dry in dryar 4 than crystals produced by conventional calcium hypochlorite techniques. In prior art techniques, more ~7~
C-6645 expensive high speed titanium centri~uges are necessary to obtain crystals of equivalent purity.
Moist cake from cake separator 3 contains from about 40 to about 60 percent by weight of Ca(OCl)2 ~ 2H2O, from about 2 to a~out lS percent by weight of NaCl, and from about 40 to 50 percent by weight of water. This moist cake may be used ~irectly in the treatment of water systems such as swimming pools and the like, but is generally dried and stored prior to use. The moist cake is dried by known means, for example, using a spray dryer, turbodryer or vacuum dryer where the appropriate temperature ranges are employed to reduce the water content to the desired level.
In the process of the present invention, the cake is dried, for example in a turbodryer with hot air while maintaining the product temperature in the range from about 35 to about 110C, and preferably from about 40 to about 95C to give a product having a calcium hypochlorite content from about 65 to about 85, a water content below about 10 percent by weight and the bulk of the remainder being sodium chloride.
Pas~e liquor from cake separator 3 generally has a sodium chloride concentration ranging from about 15 to ; about 22 percent, and preferably from about 17 to about 20 percent by weight, a calcium hypochlorite concentration ranging ~rom about 7 to about 15 percent and preexably ~rom about 8 to about 12 percent by weight, and a water content ranging from about 60 to about 75 percent and preferably ~rom about 68 to about 73 pexcent by weight.
3 ~7~
C-6645 As indicated in the third embodiment, a portion of the paste liquor may be recycled to mixing zone l, if desired, to improve control of the chl.orination and heat transfer in slurry chlorinator 2. Generally, from 0 to about 40 and preferably from about 0 t:o about 10 percent by weight of the pasteliquor is recycl.ed to mixing zone l, the balance being conveyed to caust.ic reactor 5.
As discussed above, a concentrated alkali is diluted to about 10 to 20 percent in dilution tank 6 with lime slurry from caustic reactor 5, and paste liquor is then reacted with this alkaline slurry in caustic reactor 5 to precipitate lime and a small proportion of hemi-basic calcium hypochlorite crystals. The resulting lime slurry is conveyed to lime separator 8. The lime slurry is separated in lime separator 8 to form a wet lime cake and a . .
mother liquor containing from about 7 to about 20 and preferably from about 8 to about 15 percent by weight of sodium hypochlorit~ and from about 15 to about 22 and prefer-ably from about 17 to about 20 percent by weight of sodium chloride. This mother liquor may be sold as bleach liquor but is preferably conveyed to the evaporator-chlorinator as described above, wherein it is reacted with chlorine and sodium hydorxide and evaporated to effect precipitation of sodium chloride. Sodium chloride is separated from the resulting solution in the salt sepaxator and may be used to prepare a brine feed for electrolytic cells. The resulting aqueous solution from the salt separator contains from about 15 to about 40 and preferably from about 18 to about 35 pexcent by weight of sodium hypochlorite and from . .
- .
C-6645 about 4 to about 14 and preferably from about 4 to about 8 percent by weight of sodium chloride.
Recovered lime cake, after washing, from lime separator 8 is recycled as recycled lime to mixing zone 1.
Recycled lime contains from about 25 to about 50 and pre-ferably from about 35 to about 45 perc:ent by weight o ~olid lime having a purity of from about 85 perc~nt to about 100 percent by weight of active limet The lower part of this purity range is obtained when higher propor-tions of calcium hypochlorite-hemi-basic crystals are co-precipitated. However, more concentrated lime slurries or cakes may be recovered from lime separator 8, if desired.
The process of the present invention is preferably carried out on a continuous basls which permits higher rates of chlorination and thus increased rates of production.
Continuous chlorination also produces calcium hypochlorite dihydrate crystals which are more easily separated by the solid-liquid method of separation employed and which are easier to dry.
The reaction conditions during the chlorination steps have been described above. Ganerally, the evaporation steps are carried out at temperatures ranging ~rom about 18 to about 45C and at pressures ranging from about 15 to about 35 mm Hg. All of the other steps of the process are carried out at ambient pressure and temperature conditions.
~0~ 86`
C 6645 Various operating problems occurring during ~atch chlorination are aliminated, Lime for this process does not need to he the high purity lime needed for most con-ventional commercial processes and therefore lime from virtually any source can ~e employed.
The following examples are presented to illustrate the invention more fully. All parts and percentages are by weight unless otherwise specified.
. . .
Using the process illustrated in Figure 1, 5146 parts per hour of a solution containing 27.97 percent NaOCl were admixed in mixing zone 1, an agitated vessel, with 4058 parts per hour of an aqueous lime slurry containing 30.2 percent active lime,. The slurry was prepared from 1270 parts per hour of raw lime containing g6.5 percent Ca(O~)2 (the balance being silica, iron oxide, aluminum oxide and the like~, and 369 parts per hour of recycled precipitated lime from lime separator 8 as a 35 percent lime cake, The mixture was blended in the mixing zone to form a slurry, which was transferred to slurry chlorinator 2 where 1561 parts per hour of liquid chlorine were added while the slurry was thoroughly agitated and the temperature maintained at about 30C. The calcium hypochlorite paste which formed in slurry chlori-nator 2 contained calcium hypochlorite dihydrate crystals in an aqueous NaCl solution. This paste was withdrawn from the slurry chlorinator at the rate of about 11381 parts per hour. The paste contained 26.05 percent Ca(OCl)2, 15.16 percent NaCl and 56.67 p0rcent ~2 The remainder was chlorate (0.5~ percent) and inert ingredients (1.08 percent).
The feed rate of mixing zone slurry and chlorine and the withdrawal rate of paste from slurry chlorinator 2 were adjusted to maintain concentration of free alkali in slurry ; chlorinator 2 of less than about 0.5 percent.
The resulting paste was conveyed to cake separator 3, which was a filter, where the paste was separated into a moist cake and a paste liquor. The crystals of the calcium hypochlorite dihydrate in the moist cake were flat platelets -, . . - . ' : ~
~0~ 6 C-6645 of a few microns in thickness and sides which ranged fro~
about 50 to about 300 microns in length with about 70 to about 90 percent of the crystals being larger khan 100 microns in length.
Moist cake was removed from the filter at a rate of 4762 parts per hour. The moist cake, which contained 46.26 percent Ca(OCl)2, 9.43 percent NaCl and 42.~2 percent H~O, the remainder being chlorates (0.34 percent) and inert ingredients (0.67 percent~, was transferred to a dryer and dried with hot air while maintaining the product tempera-ture inthe range of from 45 to 90~C. A dried calcium hypochlorite product was recovered from the dryer at the rate of 2451 parts per hour, containing about 74.7 percent Ca(OCl)2, 18.6 percent NaCl and having a water content of less than 1 percent, the balance being calcium chloride ~0.5), calcium chlorate (0.9), calcium hydroxide (2.1), and calci~m car-bonate (2.2). From the filter, 6369 parts per hour of paste liquor containing about 10.15 percent Ca(OCl)2, 19.68 percent NaCl and 67.57 percent H2O were recovered and trans-ferred to a caustic reactor 5. In caustic reactor 5, paste liquor was reacted with 2800 parts per hour of an a~ueous alkaline lime slurry. This alkaline lime slurry was pre-pared by recycling 1943 parts per hour of the lime slurry ormed in caustic reactor 5 to dilution tank 6, where it was admixed with 857 parts per hour of a 50 percent aqueous sodium hydroxide solution to form an alkaline lime slurry in which the solution component of the slurry cont:ained about 15.3 percent by weight of sodium hydroxide. Suffi-cient alkaline lime slurry from dilution tank 6 was fed to .~:
7~6 C-6645 caustic reactor 5 with the paste liquo:r to maintain a pH
of 12.07 in the solution component of the lime slurry and caustic reactor 5.
Lime slurry from caustic reactor S was conveyed at the rate of 7264 parts per hour to a f.ilter, which served as lime separator 8, where the slurry was separated into a mother liquor and a lime cake containing some h~mi-basic calcium hypochlorite crystals. The lime cake was washed with water and recycled to mixing zone 1. Analyses of the mother liquor, the unwashed lime cake and the washed lime cake were as follows:
Perc0nt by Wei~ht Mother U~3~b ~ Washed Lime Cake Liquor ca(OCl)2 3.8~I 4.23 0 Ca(OH)~ 30.41 32.85 0.07 NaOCl 6.96 0.16 9.5 NaCl 11.44 1.25 16.67 H2O 47.35 61.50 73.63 NaOH 0.13 pH 12.07 When 300 ccs. o the lime slurry produced in caustic reactor 5 was filtered on a fritted ylass filter under a vacuu~ of 23 inches o mercury, 2 minutes and 26 seconds were required to complete the filtration, which was equivalent to a filtration of about 0.487 gallons per hour per square foot.
~36-.~ ~ .. .. .
C-6645 For purposes of comparison the procedure of this example was repeated except that the pH of caustic reactor was maintained above about 14, which has an excess caustic concentration of 1.63 percent NaOH, which preverlted the formation of hemi-basic calcium hypochlorite crystals in the lime slurry. Filtering 300 ~cs. of the resulting lime slurry in the same kype of fritted glass filter required 39 minutes and 10 seconds to complete the filtration, which was equivalent to a filtration rate of about 0.030 gallons per hour per square foot.
: The moist lime cake from the filter 8 was recycled . .
to mixing 20ne 1.
Clarified mother liquor was recovered from lime separator 8 at the rate of about 6649 parts per hour, and stored for use as a liquid bleach.
~37~
Figure 1 is a flow sheet of a preferred embo~iment of the present invention showing the separation of calcium hypochlorite and precipitation of lime from the paste liquor.
More in detail, in the process of Figure 1, lime (both fresh lime and recycle lime of the type described more fully below), water and sodium hypochlorite are admixed in mixing `~ zone 1 to form a mixing zone slurry~ Mixing zone 1 is a mixing tank or other suitable container with agitation means for blending the various components fed thereto. There may be some degree of reaction between the various components fed to mixing zone 1, but an important function of mixing zone 1 is to admix the components, and therefore it is referred to as a "mixing zone", even though some "reaction" may occur in some embodiments of the inventionO
The resulting mixing zone slurry is conveyed to slurry chlorinator 2 and reacted with chlorine. Slurry chlorinator 2 is any suitable chlorination apparatus provided with ' , ~ . : . ~, 1~7~(1336 C-6645 agitation means for maximum contact ~etween chlorine and slurry. It is preferred to employ as slurry chlorinator 2 an evaporator chlorinator which utilize~ the chlorination technique described in U.S. Patent No. 3,241,912, issued to Bernard H. Nicolaisen on March 22, 1966. Tempera~ure within slurry chlorinator 2 is main~ai.ned within the range from about 0 to about 50 and preferably from about 20 to about 32C.
During chlorination of the slurry in slurry chlori-nator ~, lime reacts with chlorine to form calcium hypo-chlorite in accordance with Equation (1):
tl) Ca(OH)2 ~ ~12 ~ 1/2 Ca(ClO)2 + H2O ~ 1/2 CaC12 Some sodium hydroxide may be present in the mixing zone slurry as a result of feeding sodium hydroxide ~not shown) to mixing ~one 1, or it may be present in the recycle lime fed to a mixing zone 1. Any sodium hydroxide :
present in the sluxry chlorinator 2 ic reacted with chlorine to form sodium hypochlorite in accordance with ; Equation (2):
(2) 2NaOH ~ C12 ~ NaClO ~- NaCl + H2O
Sodium hypochlorite present in slurry chlorinator 2 reacts with calcium chloride to form sodium chloride and additional calcium hypochlorite in accordance with Equation (3):
: (3) NaClO ~ 1/2 CaC12 ~ 1/2 Ca(ClO)2 ~ NaCl :~ -13-.. . . . .
C-6645 The primary products of slurry chlorinator 2 are calcium hypochlorite, sodium chloride and water. At start-up of the process, it is preferred, but not necessary to fill slurry chlorinator 2 with a sluxry or "paste" of calcium hypochlorite solids suspended in an aqueous solution of sodium chloride and calcium hypochlorite, with an excess alkali concentration in the slurry being less than about 1.0 and pre~erably less than about 0.50 percent by weight. The rate of feed of mixing zone slurry and chlorine to slurry chlorinator 2 and rate of evaporation of water, if any, are adjusted to maintain the concentxation of unreacted alkali during the reaction below about 1.0 percent. Continuous chlorination of the slurry in this manner causes the formation of coarse calcium hypochlorite dihydrate crystals which are : much more easily separated fxom paste liquor in cake separator 3, than are calcium hypochlorite dihydrate crystals prepared in a conventional triple salt process or a batch type process.
A portion of the resulting "paste" comprised of solid ! calcium hypochlorite dihydrate and a "paste" liquor, which is predominately an aqueous solution of sodium chloride and calcium hypochlorite is continuously withdrawn from slurry chlorinator 2 and conveyed to cake separator 3.
Cake separator 3 is a filter, centrifuge, or other suitable solid-liquid separating apparatus capable of separating a moist cake of calcium hypochlorite dihydrate crystals from the aqueous solution o sodium chloride and calcium hypochlorite.
~L~)7~ 6 C 6645 Moist cake from cake separator 3 generally contains from about 40 to about 6C percent by weight of calcium hypochlorite dihydrate, from about 2 to about 15 percent by weight of sodi~n chloride, and from about 38 to about 52 percent by weight of water. Moist cake is generally conveyed to dryer 4 where it is heated to remove most of the water. Dryer 4 is any suitable drying unit or unit~
capable of reducing the moisture content of the oalcium hypochlorite caXe to the desired level without causing excess decomposition of the calcium hypochlorite particles.
Generally the water content of the calcium hypochlorite is reduced in dryer 4 to below about 10 percent by weight and preferably from about 0.5 to about 7.5 percent by weight. The calcium hypochlorite content of the dried calcium hypochlorite generally ranges from about 65 to about 85, and preferably from about 70 to about 80 percent by weight. The remainder of the dried calcium hypochlorite is predominately sodium chloride. The dried product is then placed in suitable containers, with or without prior size classification or other processing such as pelletizing, prior to use in water treatment or other utility.
"Paste liquox'l (or "paste filtrate" when cake separator 3 is a filter) is an aqueous sodium chloride solution from cake separator 3 which also contains soluble calcium hypochlorite. This paste liquor is conveyed to caustic reactor 5, which is any suitable mixing tank reactor provided wi~h agitation means, where it is reacted with an aqueous solution of a soluble metal hydroxide, preferably sodium hydroxide, to form a lime slurryO
~15-~7~3~i C-6645 The aqueous solution of sodium hydroxide is prepared by admixing sodium hydroxide or other alkaline compounds in dilution tank 6 with a portion of the lime slurry from caustic reactor 5. The lime slurry is conveyed from caustic reactor 5 to dilution tank 6 by means of caustic reactor pump 7. SUfficient lime slurry is recycled to the ; dilution tank to form an alkaline aqueous slurry in which the proportion of sodium hydroxide or other soluble metal hydroxide is in the range from about 10 -to ahout 20 percent by weight.
; The recycle flow of lime slurry is preferably maintained uniform, and as the reaction requires more or less alkali to maintain the desired pH in reactor 5, the control system adds more or less caustic to the dilution tank resulting in a variation of the NaOH concentration in the dilution system.
The slurry in the caustic reactor 5 is maintained at a pH of about 11.0 to about 13.5~ and preferably from about 12 to 12.5 by incxeasing or decreasing the caustic flow to dilution tank 6.
A portion of the lime slurry is conveyed to lime separator 8 such as a filter, where the solid lime particles and the resulting hemi-basic calcium hypochlorite crystals are separated from the aqueous mother liquor, which pre-dominates in sodium chloride.
The reaction between the alkaline compound such as sodium hydroxide and the calcium hypochlorite in the paste liquor proceeds in accordance with Equations (4) and (5).
. . , , , : .
, . . . . , ,: ... .
1~'7~
C-6645 (4) 2NaOH + Ca(ClO)2 -- ~ Ca(OH)2 ~ 2NaClO
(5) 1/2 Ca(OH)2 ~ Ca(OCl)2 ) Ca(OCl)2 1/2 Ca (~)2 The crystals of lime and hemi-basic calcium hypo-chlorite crystals in the cake formed i:n lime separator 8 are easily washed with water to remove excessive salt from the lime cake and the washed cake is recycled to mixing zone 1.
Mother liquor, the aqueous solution of sodium chloride and sodium hypochlorite recovered in lime separator 8, may be utilized as bleach liquor. This mother liquor contains essentially no calcium hypochlorite values. Therefore, a much larger percentage of lime fed into the system is recovered as large crystals Qf calcium hypochlorite dihydrate rather than as an impurity in an effiuent stream or sold as a less expensive bleach liquor. However, mother liquor from lime separator 8 is preferably recycled to ~he proces~ as described more fully below.
In a second embodiment of the invention an aqueous solution of sodium chloride and sodium hypochlorite from lime separator 8 i9 conveyed to an evaporator-chlorinator ~not shown~ where the aqueous solution is concentrated by evaporation and is reacted with sodium hydroxide and chlorine to form a slurry of solid sodium chlorlde in an aqueous solution of sodium hypochlorite.
8~
C-6645 This evaporation and reaction is carried out in any suitable evaporation apparatus and chlorinator-reactor provided with agitation means. Simultaneous evaporation and chlorination may be carried out in an evaporative chlorinator using the chlorination technique described in U.S. Patent No. 3,241,912, issued to Bernard H. Nicolaisen on March 22, 1966.
: In a preferred embodiment of the invention, the mother liquor is first concentrated.by evaporation with steam, in an evaporator (not shown) and the resulting con-centrated mother liquor is then reacted with chlorine and sodium hydroxide in the evaporator-chlorinator, utilizing the heat of chlorination to complete evaporation of the mother liquor and effect precipitation of salt in the mother liquor.
Evaporation prior to reaction in the evaporator-chlorinator is generally more economical since the rate of evaporation of water is more rapid from the dilute mo~her liquor prior to reacting and therefore smaller, less expensive evaporatoxs may be used than are required ~or the more concentrated slurry of salt and mother liquorO .~:
In another embodiment o~ the invention~ no chlorine .
or sodium hydroxide are added to the evapora~or-chlorinator and only evaporation takes place in the evaporator-chlorinator to effect precipitation of salt in the mother liquor. The degree of evaporation will depend upon the .
initial mother liquor concentration, C-6645 When chlorination is used, the temperature during chlorination is generally maintained within the range from about 0 to a~out 50 and preferably from about 20 to about 32C.
In this embodiment, sufficient chlorine and sodium hydroxide are added to and sufficient water is removed from the mother liquor fed to the evaporator-chlorinator to maintain in the solution portion of the resulting slurry a sodium hypochlorite concentration within the range from about 15 to about 40 and preferably from about 25 to about 35 percent by weight. In addition, the soluble soclium chloride concentration in the solution portion of the slurry from evaporator-chlorinator is maintained from about 4 to about 14 and preferably from about 4.8 to about 7.7 percent be weight. The solid sodium chloride concentration in '' the slurry from the evaporator~chlorinatox ranges from a~out 15 to about 35, and preerably rom about 18 to about 28 percent by weight. The resulting slurry i9 conveyed to a , salt separator (not shown) which is a suitable filker, centrifuge or similar solid-liquid separating apparatus.
In the salt separator, relatively pure sodium chloride crystals are separated from the aqueous sodium hypochlorite solution. These crystals may be used in the preparation of br,ine which is used as a feed material for electrolytic cells used in the preparation of chlorine and sodium hydroxide.
~19-C-66~5 The aqueous solution of sodium h~pochlorite which is also separated from the salt separator~ is recycled to mixing zone 1 for further admixing with fresh lime and recylced lime.
This embodiment of the invention not only results in easily filtexable lime, large crystals of hemi-basic calcium hypochlorite and more efficient utilization of calcium values as calcium hypochlorite, as in the embodiment of Figure 1, but also produces relatively pure sodium chloride in solid form, which has utility in the preparation of brine feed for electrolytic cells. There are no impure aqueous solutions of sodium chloride, calcium hypochlorite or the like which need to be disposed of in the latter embodiment thereby avoiding a seriou~ pollution pro~lem.
A third em~odiment of the invention includes the second embodiment above as well as a technique for purifying at least a portion of the fresh lime fed to the p~ocess prio~ to admixing with sodium hypochlorite in mixing zone 1 and recycling at least a portion of the paste liquor to mixing zone 1.
1Ci7q;~
C-6645 In the third embodiment, an aqueous slurry of fresh lime is chlorinated in lime chlorinator (not shown) to form an aqueous solution of calcium hypochlorite and calcium chloxide in accordance with Equation (1). Impurities in the fresh lime include insoluble impurities such as silica, aluminum salts, iron salts, magnesium ~alts, magnesia, unburned limèstone (calcium carbonate and magnesium caxbonate) and other compounds in ~race quantities. The~e impurities present in the fresh lime remain insoluble in the aqueous solution formed in the lime chlorinator and form a slurry with the.aqueous solution of calcium hypo-chlorite and ~alcium chloride. This slurry is conveyed to an impurity separator (not shown), which is a suitable solid-liquid separator such as a filter, centrifuge or the like, where solid impurities are separatedO Solid impurities ~rom the impurity separator are generally disposed of as solid waste, land fill or the like. The aqueous solution of calcium hypochlorite and calcium chloride from the impurity separator is conveyed to mixing zone 1. As indicatPd above, the primary function of mixing zone 1 is to ef~ect admixing of the components fed thereto. However, in the third embodiment~ the calcium chloride component of the aqueous solution from the impurity separator is reacted in mixing zone 1 with sodium hypochlorite to ~orm an aqueous : .
.
~70~)8~i C-6645 solution of calcium h~pochlorite and sodium chloride in accordance with Equation t3~.
In the third emhodiment, at least a portion of the fresh lLme is purified in the lime chls)rinator and impurity separator prior to feeding to mixing zone 1, and a portion of the fresh lime fed to mixing zone 1 may be untreated.
The ratio of fresh lime in each of these feed streams depends upon the initial purity and activity of the fresh lime fed to the process as well as specifications for " 10 impurities required for the calcium hypochlorite productO
Thus, if the fresh lime i5 relatively pure and the ~tandards for purity of the calcium hypochlorite are not high, then little or no fresh lime has to be purified prior to feeding to mixing zone 1. However, if the lime is relatively impure, then a large fraction or all of the ~resh lime is ~ :
purified in the lime chlorinator and impurity separator prior to feeding to mixing zone 1.
In all of the above defined embodiments, in order to maintain within the mixing zone slurry the concentration of lime (both fresh lime, if added, and recycled lime) within the desired range, and the concentration of sodium hypochlorite within the desired range, additional sodium hydroxide may be added to mixing zone 1. In addition, in order to improve control of the chlorination and heat transfer in slurry chlorinator 2 a portion of the paste liquor from cake separator 3 may be recycled to mixing zone 1.
, C-6645 The primary raw materials for the pro~e~s of this invention are lime, sodium hydroxide, chlorine cmd water.
Fresh lime is added to the process at mixing zone 1 and~or the lime chlorinator. One of the advantages of a preferred embodiment of this invention is that relatively impure lime may be utilized to prepare a relatively pure calcium hypochlorite product. For example, lime having an active lime content as low as 85 percent by weight or less may be added to the lime chlorinator in accordance with the third embodiment of this invention, and procluce a relatively pure calcium hypochlorite product. Generally the active lime content of the lime fed to the lime chlorinator and/or mixing zone 1 ranges from about 85 to about 100 percent, and preferably from about 90 to about 97 p rcent by weight of active lime. Lime impurities of the type described above may range from about n to about 15 percent and generally from about 3 to about 10 percent by weight of the lime.
Typical illustrative specifications for a preferred ~ -fresh lime feed and for an acceptable lime feed are as follows:
Component Preferred Acceptable C~(OH)2 min.% g5.0 85 CaCO3 max.~ 1.0 3.0 MyO max.% 0.5 3~5 SiO~ max.~ 0.5 2.5 Fe2O3~A12O3 max.~ 0.5 1.5 CaSO4 max.~ 0.5 1.5 -2~-. . , . . :
v~
C-6645 Generally from 0 to less than about 1~2 of the lime feed ; meeting the above-illustrative preferxed specifications does not need to be processed in accordance with the lime purification embodiment of the third embodiment. However, when processing lime feed meeting the above illustrative acceptable specifications a major portion up to all of the feed may have to be processed in accordance with the lime purification step of the third embodiment. The average particle size of fresh lime added to the process generally is substantially all -325 mesh (wet screen analy~is) but particles up to about ~~00 mesh may be employed if desired.
When the impurity content of lime in the lime feed is greater than about S percent by weight, it may be desirable to add the lime chlorinator a carbonating agent such as carbon dioxide or sodium carbonate to enhance precipita-tion and removal of the impurities in solid form from impurity separator 10.
As indicated above, fresh lime is fed to the system either through the lime chlorinator or mixing zone 1, or a combination of both. It is preferred to feed-from about 25 to about 100 percent of the fresh lime into the lim~ chlorinator and any balance of fresh lime being fed into mixing zone 1. When all of the fre~h lime is fed to the lime chlorinator then substantially all of the lime fed to mixing zone 1 is in the form of recycle lime slurry, the concentrated slurry of precipitated lime.
Fresh lime is fed to the lime chlorinator as an aqueous slurry containing from about 10 to about 30 percent, and C~6645 preferably ~rom about 15 to about 20 percent by weight of active lime. Into mixing zone 1, lime may be added dry or as a slurry up to about 50 percent lime by weight, Lime added to mixing zone 1 as recycle lime rom lime separator 8 is substantially pure lime~ having an active lime content of from about 85 to about 100 percent by weight. The solid content of the recycle lime slurry generally ranges from about 20 to about 50 and preferably from about 25 to about 35 percent by weight of solids, which are predominately lime, and containing some hemi-basic cryskals of calcium hypochlorite.
Sodium hydroxide is added to dilution tank 6, the evaporator chlorinator and if desired, to mixing zone 1, as a concentrated aqueous solution, generally ranging from about 40 to about 60 percent by weight of sodium hydroxide. However, sodium hydroxide may be added in anhydrous form to dilution tank 6 and the evaporator-chlorinator, and if desired, to mixing zone 1.
In addition, sodium hypochlorite added to mixing ~one 1 in Figure 1 may be prep~red by chlorinating an a~ueous solution of sodium hydroxide, in a suitable agitated chlorinator reactor (not shown). The sodium hydroxide concentration in the aqueous solution used to make sodium hypochlorite for feed to mixing zone 1 of Figure 1 ranges from about 20 to about 75 and preferably fromabout 35 to about 5S percent by weight. In the second and third embodiments, sodium hypochlorite solution is added to the mixing zone as a recycle stream from the ~alt separator. Concen~ration of this recycle stream by ~2~-. .
~7~
.
C-6645 evapoxation in the evaporator-chlorinator is generally sufficient to maintain the desired sodium hypochlorite concentration in mixing zone l. However, if desired, any necessary additional sodium hydroxide may be added dire¢tly to mixing zone 1 or additional sodium hypo-chlorite may be prepared by chlorinating an aqueous solution of sodium hydroxide and then addad to mixing zone 1 as described above with respect to Figure 1, or may be added to mother liquor prior to or simultaneous with chlorination in the evaporator-chlorinator.
The overall reaction for the process of this invention may be illustrated by Equation ~6):
~6) Ca(OH)2 + 2C12 + 2NaOH ~ Ca~ClO)2 ~ 2NaC1 ~ 2H2O
Thus, the stoichiometric proportion of fresh sodium hydroxide fed to the process is equivalent to two moles of sodium hydroxide per mole of active lime present in the fresh lime fed to the process. As indicated in the embodiment of Figure 1, sodium hydroxide is fed to caustic reactor 5 and may be used to form sodium hypochlorite fed to mixing zone 1. In the second embodiment, sodium hydroxide is added to caustic reactor S and the evaporator-chlorinator (not shown).
In the third embodiment, sodium hydroxide is added to caustic reactor 5, and to either the evaporator-chlorinator or mixing zone 1, or both. The relative ratio of proportions of sodium hydroxide added to the di~ferent units of the di~ferent embodimen~s may be varied over a wide range.
Generally, above about 20 and preferably ~rom about 22 to `
.
0~8~
C-6645 about 35 percent o~ the stoichiometric proportion of sodium hydroxide required in Equation (6~ is added to caustic reactor 5 to precipitate lime and hemi~basic calcium hypo-chlorite crystals from the paste liquor. The balance of the stoichiometric proportion of sodium hydroxide is added in the embodiment of Figure 1 as sodium hypochlorite to mixing zone 1. The balance of sodium hydroxide is added to the evaporator-chlorinator in the second embodiment.
The balance o sodium hydroxide is added either entirely to evaporator-chlorinator in the thixd embodiment, or up to about 70 percent of the balance of the stoichio-metric proportion may be added to mixing zone 1.
In the embodiment of Figure 1 and the second embodi-ment where lime ~both fresh and recycled) and sodiwm hypochlorite solution are added to mixing zone 1, the resulting mixing zone slurry has a lime concentration ranging from about 1 to about 25 and preferably from about 2 to about 20 weight percent and a sodlum hypochlorite concentration ranging from about 1.5 to about 30, and : 20 preferably from about 2 to about 26 percent by weight. In the third embodiment, when all or part of the fresh lime is purified in the lime chlorinator and impurity separator to form an aqueous solution of calcium hypochlorite and calcium chloride which is fed to mixing zone 1~ the resulting mixing zone slurry has a lime concentration and sodium hypochlorite concentration within the above ranges as well as a concentration of calcium hypochlorite ranging from a~out 0 to about 30, and preferably from about 5 to about 26 percent by weight. All of the calcium chloride fed to .
~C~7~
C-6645 mixing zone 1 re~cts with sodium hypochlorite to form calcium hypochlorite and sodium chloride in acco.rdance with Equation (3).
The ultimate water content in the mixing zone slurry is controlled by adjusting the water content of the various feed streams to mixing zone 1. For example, the water content of the aqueous solution of calcium hypochlorite and calcium chloride (when lime purification of the third embodiment is used), the water content of any lime slurry added, ~either fxesh or recycled lime) the water content of the sodium hypochlorite (either fresh sodium hypo-chlorite or recycled), and.if desired, the quantity of re-cycled paste liquor from cake separator 3 are controlled to obtain a mixing zone slurry of the desired concentration range described above.
.As indicated above, slurry-chlorinator 2 at start-up, is preferably filled, but not necessarily filled, with a slurry of calcium hypochlorite solids suspended in an aqueous solution of sodium chloride. The excess lime or other alkali in the slurxy is maintained below about 1.0 and preferably less than about 0.5 percent by weight of the sluxry. The feed xate of mixing zone slurry and chlorine to mixing slurry chlorinator 2 and the withdrawal rate of the resulting calcium hypochlorite paste are adjusted to achieve substantially complete chlorination of the calcium hydroxide values fed to slurry chlorinator 2 in mixing zone slurry, while maintaining the free lime or alkali conce.ntration in slurry chlorinator 2 preferably below about 1.0 percent by weight of the slurry.
~7(~
C-6645 Chlorine is added to slurry chlorinator 2 as well as the evaporator-chlorinator and lime chlorinator in either gaseous or liquid form. The chlorination reactions are carried out preferably continuously in an evaporator type chlorinator of the type described above.
Paske from slurry chlorinator 2 is predominately a slurry of calcium hypochlorite dihydrate in an aqueous solution of sodium chloride and calcillm hypochlorite~ The paste contains calcium hypochlorite dihydrate crystals in the concentration of from about 10 to about 35 and preferably from about 15 to about 30 percent by weight. These crystals are predominately rectangular platelets which are several microns in thickness, and have substantially equal sides ranging from about 50 to about 300 microns in length with the major portion haviny sides ranginy from about 100 microns to about 250 microns in length. Generally, less than about 5 percent of the crystals are "twin crystals"
which entrain paste liquor, which are difficult to separate from the paste liquor, ancl which are difficult to dry.
Since more than about 95 percent of the calcium hypochlorite dihydrate crystals obtained by the process of this invention may be large platelets or cohesive agglomerates, there is a minimal amount of paste liquor entrained in the crystals during the separation in cake separator 3, even when filtered on a drum filter. The crystals are easier to separate from the paste liquor in cake separator 3 and are easier to dry in dryar 4 than crystals produced by conventional calcium hypochlorite techniques. In prior art techniques, more ~7~
C-6645 expensive high speed titanium centri~uges are necessary to obtain crystals of equivalent purity.
Moist cake from cake separator 3 contains from about 40 to about 60 percent by weight of Ca(OCl)2 ~ 2H2O, from about 2 to a~out lS percent by weight of NaCl, and from about 40 to 50 percent by weight of water. This moist cake may be used ~irectly in the treatment of water systems such as swimming pools and the like, but is generally dried and stored prior to use. The moist cake is dried by known means, for example, using a spray dryer, turbodryer or vacuum dryer where the appropriate temperature ranges are employed to reduce the water content to the desired level.
In the process of the present invention, the cake is dried, for example in a turbodryer with hot air while maintaining the product temperature in the range from about 35 to about 110C, and preferably from about 40 to about 95C to give a product having a calcium hypochlorite content from about 65 to about 85, a water content below about 10 percent by weight and the bulk of the remainder being sodium chloride.
Pas~e liquor from cake separator 3 generally has a sodium chloride concentration ranging from about 15 to ; about 22 percent, and preferably from about 17 to about 20 percent by weight, a calcium hypochlorite concentration ranging ~rom about 7 to about 15 percent and preexably ~rom about 8 to about 12 percent by weight, and a water content ranging from about 60 to about 75 percent and preferably ~rom about 68 to about 73 pexcent by weight.
3 ~7~
C-6645 As indicated in the third embodiment, a portion of the paste liquor may be recycled to mixing zone l, if desired, to improve control of the chl.orination and heat transfer in slurry chlorinator 2. Generally, from 0 to about 40 and preferably from about 0 t:o about 10 percent by weight of the pasteliquor is recycl.ed to mixing zone l, the balance being conveyed to caust.ic reactor 5.
As discussed above, a concentrated alkali is diluted to about 10 to 20 percent in dilution tank 6 with lime slurry from caustic reactor 5, and paste liquor is then reacted with this alkaline slurry in caustic reactor 5 to precipitate lime and a small proportion of hemi-basic calcium hypochlorite crystals. The resulting lime slurry is conveyed to lime separator 8. The lime slurry is separated in lime separator 8 to form a wet lime cake and a . .
mother liquor containing from about 7 to about 20 and preferably from about 8 to about 15 percent by weight of sodium hypochlorit~ and from about 15 to about 22 and prefer-ably from about 17 to about 20 percent by weight of sodium chloride. This mother liquor may be sold as bleach liquor but is preferably conveyed to the evaporator-chlorinator as described above, wherein it is reacted with chlorine and sodium hydorxide and evaporated to effect precipitation of sodium chloride. Sodium chloride is separated from the resulting solution in the salt sepaxator and may be used to prepare a brine feed for electrolytic cells. The resulting aqueous solution from the salt separator contains from about 15 to about 40 and preferably from about 18 to about 35 pexcent by weight of sodium hypochlorite and from . .
- .
C-6645 about 4 to about 14 and preferably from about 4 to about 8 percent by weight of sodium chloride.
Recovered lime cake, after washing, from lime separator 8 is recycled as recycled lime to mixing zone 1.
Recycled lime contains from about 25 to about 50 and pre-ferably from about 35 to about 45 perc:ent by weight o ~olid lime having a purity of from about 85 perc~nt to about 100 percent by weight of active limet The lower part of this purity range is obtained when higher propor-tions of calcium hypochlorite-hemi-basic crystals are co-precipitated. However, more concentrated lime slurries or cakes may be recovered from lime separator 8, if desired.
The process of the present invention is preferably carried out on a continuous basls which permits higher rates of chlorination and thus increased rates of production.
Continuous chlorination also produces calcium hypochlorite dihydrate crystals which are more easily separated by the solid-liquid method of separation employed and which are easier to dry.
The reaction conditions during the chlorination steps have been described above. Ganerally, the evaporation steps are carried out at temperatures ranging ~rom about 18 to about 45C and at pressures ranging from about 15 to about 35 mm Hg. All of the other steps of the process are carried out at ambient pressure and temperature conditions.
~0~ 86`
C 6645 Various operating problems occurring during ~atch chlorination are aliminated, Lime for this process does not need to he the high purity lime needed for most con-ventional commercial processes and therefore lime from virtually any source can ~e employed.
The following examples are presented to illustrate the invention more fully. All parts and percentages are by weight unless otherwise specified.
. . .
Using the process illustrated in Figure 1, 5146 parts per hour of a solution containing 27.97 percent NaOCl were admixed in mixing zone 1, an agitated vessel, with 4058 parts per hour of an aqueous lime slurry containing 30.2 percent active lime,. The slurry was prepared from 1270 parts per hour of raw lime containing g6.5 percent Ca(O~)2 (the balance being silica, iron oxide, aluminum oxide and the like~, and 369 parts per hour of recycled precipitated lime from lime separator 8 as a 35 percent lime cake, The mixture was blended in the mixing zone to form a slurry, which was transferred to slurry chlorinator 2 where 1561 parts per hour of liquid chlorine were added while the slurry was thoroughly agitated and the temperature maintained at about 30C. The calcium hypochlorite paste which formed in slurry chlori-nator 2 contained calcium hypochlorite dihydrate crystals in an aqueous NaCl solution. This paste was withdrawn from the slurry chlorinator at the rate of about 11381 parts per hour. The paste contained 26.05 percent Ca(OCl)2, 15.16 percent NaCl and 56.67 p0rcent ~2 The remainder was chlorate (0.5~ percent) and inert ingredients (1.08 percent).
The feed rate of mixing zone slurry and chlorine and the withdrawal rate of paste from slurry chlorinator 2 were adjusted to maintain concentration of free alkali in slurry ; chlorinator 2 of less than about 0.5 percent.
The resulting paste was conveyed to cake separator 3, which was a filter, where the paste was separated into a moist cake and a paste liquor. The crystals of the calcium hypochlorite dihydrate in the moist cake were flat platelets -, . . - . ' : ~
~0~ 6 C-6645 of a few microns in thickness and sides which ranged fro~
about 50 to about 300 microns in length with about 70 to about 90 percent of the crystals being larger khan 100 microns in length.
Moist cake was removed from the filter at a rate of 4762 parts per hour. The moist cake, which contained 46.26 percent Ca(OCl)2, 9.43 percent NaCl and 42.~2 percent H~O, the remainder being chlorates (0.34 percent) and inert ingredients (0.67 percent~, was transferred to a dryer and dried with hot air while maintaining the product tempera-ture inthe range of from 45 to 90~C. A dried calcium hypochlorite product was recovered from the dryer at the rate of 2451 parts per hour, containing about 74.7 percent Ca(OCl)2, 18.6 percent NaCl and having a water content of less than 1 percent, the balance being calcium chloride ~0.5), calcium chlorate (0.9), calcium hydroxide (2.1), and calci~m car-bonate (2.2). From the filter, 6369 parts per hour of paste liquor containing about 10.15 percent Ca(OCl)2, 19.68 percent NaCl and 67.57 percent H2O were recovered and trans-ferred to a caustic reactor 5. In caustic reactor 5, paste liquor was reacted with 2800 parts per hour of an a~ueous alkaline lime slurry. This alkaline lime slurry was pre-pared by recycling 1943 parts per hour of the lime slurry ormed in caustic reactor 5 to dilution tank 6, where it was admixed with 857 parts per hour of a 50 percent aqueous sodium hydroxide solution to form an alkaline lime slurry in which the solution component of the slurry cont:ained about 15.3 percent by weight of sodium hydroxide. Suffi-cient alkaline lime slurry from dilution tank 6 was fed to .~:
7~6 C-6645 caustic reactor 5 with the paste liquo:r to maintain a pH
of 12.07 in the solution component of the lime slurry and caustic reactor 5.
Lime slurry from caustic reactor S was conveyed at the rate of 7264 parts per hour to a f.ilter, which served as lime separator 8, where the slurry was separated into a mother liquor and a lime cake containing some h~mi-basic calcium hypochlorite crystals. The lime cake was washed with water and recycled to mixing zone 1. Analyses of the mother liquor, the unwashed lime cake and the washed lime cake were as follows:
Perc0nt by Wei~ht Mother U~3~b ~ Washed Lime Cake Liquor ca(OCl)2 3.8~I 4.23 0 Ca(OH)~ 30.41 32.85 0.07 NaOCl 6.96 0.16 9.5 NaCl 11.44 1.25 16.67 H2O 47.35 61.50 73.63 NaOH 0.13 pH 12.07 When 300 ccs. o the lime slurry produced in caustic reactor 5 was filtered on a fritted ylass filter under a vacuu~ of 23 inches o mercury, 2 minutes and 26 seconds were required to complete the filtration, which was equivalent to a filtration of about 0.487 gallons per hour per square foot.
~36-.~ ~ .. .. .
C-6645 For purposes of comparison the procedure of this example was repeated except that the pH of caustic reactor was maintained above about 14, which has an excess caustic concentration of 1.63 percent NaOH, which preverlted the formation of hemi-basic calcium hypochlorite crystals in the lime slurry. Filtering 300 ~cs. of the resulting lime slurry in the same kype of fritted glass filter required 39 minutes and 10 seconds to complete the filtration, which was equivalent to a filtration rate of about 0.030 gallons per hour per square foot.
: The moist lime cake from the filter 8 was recycled . .
to mixing 20ne 1.
Clarified mother liquor was recovered from lime separator 8 at the rate of about 6649 parts per hour, and stored for use as a liquid bleach.
~37~
Claims (20)
1. In a process for recovering lime from an aqueous solution of calcium hypochlorite wherein lime is precipitated in a reaction zone by the reaction of an alkali metal hydroxide with said aqueous solution, and recovering the solid lime particles produced thereby, the improvement which comprises reacting said alkali metal hydroxide with said aqueous solution in proportion sufficient to maintain the pH in the range from about 11 to about 13.5, whereby a mixture of crystalline particles of hemi-basic calcium hypochlorite and lime is formed.
2. The process of claim 1 wherein said pH is maintained in the range from about 12 to about 12.5.
3. The process of claim 2, wherein said alkali metal hydroxide is sodium hydroxide.
4. The process of claim 1 wherein said aqueous solution contains an alkali salt.
5. The process of claim 4 wherein said alkali salt is an alkali metal salt.
6. The process of claim 5 wherein said alkali metal salt is sodium chloride.
7. The process of claim 6 wherein said aqueous solution contains from about 5 to about 12 percent by weight of calcium hypochlorite and from about 16 to about 20 percent by weight of sodium chloride.
8. The process of claim 7 wherein said aqueous solution contains from about 9.5 to about 10.5 percent by weight of calcium hypochlorite and from about 17 to about 18 percent by weight of sodium chloride.
9. The process of claim 4 wherein said alkali salt is an alkaline earth metal salt.
10. The process of claim 9 wherein said alkaline earth metal salt is calcium chloride.
11. The process of claim 10 wherein said aqueous solution contains from about 1 to about 10 percent by weight of calcium hypochlorite and from about 15 to about 40 percent by weight of calcium chloride.
12. The process of claim 11 wherein said aqueous solution contains from about 1 to about 8 percent by weight of calcium chloride and from about 18 to about 35 percent by weight of calcium chloride.
13. The process of claim 2 wherein the residence time of said mixture in said reaction zone prior to recovering said solids from said reaction zone is from about 20 to about 180 minutes.
14. The process of claim 13 wherein said residence time is from about 25 to about 45 minutes.
15. The process of claim 3 wherein a portion of the resulting lime slurry is admixed with said sodium hydroxide prior to reacting with said aqueous solution to form an alkaline lime slurry having a solid component and a liquid component, wherein said liquid component contains from about 10 to about 20 percent by weight of sodium hydroxide, and reacting said alkaline lime slurry with said aqueous solution.
16. The process of claim 15 wherein the aqueous lime slurry formed in said reaction is formed from a liquid component and a solid component, wherein said solid component is comprised of a mixture of lime and hemi-basic calcium hypochlorite crystals wherein the ratio of said lime to said hemi-basic calcium hypochlorite crystals are in the range from about 2.5:1 to about 50:1.
17. The process of claim 16 wherein said aqueous solution contains from about 5 to about 12 percent by weight of calcium hypochlorite and from about 16 to about 20 percent by weight of sodium chloride.
18. The process of claim 17 wherein said residence time of said mixture in said reaction zone prior to recovering said solids ranges from about 20 to about 180 minutes.
19. The process of claim 18 wherein said residence time ranges from about 25 to about 45 minutes.
20. The process of claim 8 wherein said pH is maintained in the range from 12 to about 12.5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59023075A | 1975-06-25 | 1975-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1070086A true CA1070086A (en) | 1980-01-22 |
Family
ID=24361389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA254,350A Expired CA1070086A (en) | 1975-06-25 | 1976-06-08 | Lime recovery process |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS524497A (en) |
| AU (1) | AU505885B2 (en) |
| BE (1) | BE843442A (en) |
| BR (1) | BR7604051A (en) |
| CA (1) | CA1070086A (en) |
| DE (1) | DE2628062A1 (en) |
| ES (1) | ES449125A1 (en) |
| FR (1) | FR2317228A1 (en) |
| GB (1) | GB1524119A (en) |
| IT (1) | IT1066160B (en) |
| NL (1) | NL7606952A (en) |
| ZA (1) | ZA763809B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196184A (en) * | 1972-05-30 | 1980-04-01 | Olin Corporation | Lime recovery process |
| EP0108824B1 (en) * | 1982-11-13 | 1987-10-28 | L. SCHULER GmbH | Appliance for the electric resistance welding of longitudinal seams using seam squeezing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3895099A (en) * | 1972-05-30 | 1975-07-15 | Olin Corp | Process for manufacture of calcium hydrochlorite |
| JPS5418238B2 (en) * | 1973-11-28 | 1979-07-05 |
-
1976
- 1976-06-08 CA CA254,350A patent/CA1070086A/en not_active Expired
- 1976-06-15 AU AU14895/76A patent/AU505885B2/en not_active Expired
- 1976-06-21 IT IT50056/76A patent/IT1066160B/en active
- 1976-06-22 GB GB25908/76A patent/GB1524119A/en not_active Expired
- 1976-06-23 BR BR7604051A patent/BR7604051A/en unknown
- 1976-06-23 DE DE19762628062 patent/DE2628062A1/en not_active Withdrawn
- 1976-06-23 ES ES449125A patent/ES449125A1/en not_active Expired
- 1976-06-24 FR FR7619280A patent/FR2317228A1/en active Granted
- 1976-06-24 JP JP51074962A patent/JPS524497A/en active Granted
- 1976-06-25 ZA ZA00763809A patent/ZA763809B/en unknown
- 1976-06-25 BE BE168344A patent/BE843442A/en unknown
- 1976-06-25 NL NL7606952A patent/NL7606952A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| ES449125A1 (en) | 1977-07-01 |
| ZA763809B (en) | 1978-02-22 |
| IT1066160B (en) | 1985-03-04 |
| BE843442A (en) | 1976-12-27 |
| JPS5529923B2 (en) | 1980-08-07 |
| FR2317228B1 (en) | 1981-08-07 |
| FR2317228A1 (en) | 1977-02-04 |
| AU1489576A (en) | 1977-12-22 |
| NL7606952A (en) | 1976-12-28 |
| AU505885B2 (en) | 1979-12-06 |
| DE2628062A1 (en) | 1977-01-20 |
| GB1524119A (en) | 1978-09-06 |
| BR7604051A (en) | 1977-07-05 |
| JPS524497A (en) | 1977-01-13 |
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