CA1266365A - Use of surfactants in alumina precipitation in the bayer process - Google Patents
Use of surfactants in alumina precipitation in the bayer processInfo
- Publication number
- CA1266365A CA1266365A CA000563608A CA563608A CA1266365A CA 1266365 A CA1266365 A CA 1266365A CA 000563608 A CA000563608 A CA 000563608A CA 563608 A CA563608 A CA 563608A CA 1266365 A CA1266365 A CA 1266365A
- Authority
- CA
- Canada
- Prior art keywords
- oil
- surfactant
- fatty acid
- liquor
- component
- 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 - Fee Related
Links
Classifications
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/144—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
- C01F7/145—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process characterised by the use of a crystal growth modifying agent other than aluminium hydroxide seed
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/144—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates
- C01F7/47—Purification of aluminium oxide, aluminium hydroxide or aluminates of aluminates, e.g. removal of compounds of Si, Fe, Ga or of organic compounds from Bayer process liquors
- C01F7/473—Removal of organic compounds, e.g. sodium oxalate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
Abstract of the Disclosure A method and composition for producing a more coarse alumina trihydrate crystal in a Bayer process pregnant liquor, involving the addition of approximately 5-400 mg/1 of a surfactant oil mixture, the oil dissolving the surfactant which can be selected from a wide range of surfactants which are stable in (hot) caustic solutions and capable of dispersing hydrophobic liquids in the Bayer liquor. The preferred embodiment involves the use of tall-oil fatty acids; a number of equivalent surfactants are also described. The oil or hydrocarbon (hydrophobic) liquid can be selected from paraffinic oils, naphthenic oils, mineral seal oils, fuel oils, and bottoms or residue from a C10 alcohol distillation.
Description
3~5 --USE OF SURFACTANTS IN AI~UMINA
PRECIPITATION IN THE BAYER PROCESS
INTRODUCTION
_ This invention i~ concerned with treatment of a Bayer process green liquor rom which aluminum values are precipitated.
In the Bayer proce~s for Bauxite ore beneficiation, crystallization and precipitation of solubilized alumina trihydrate values from caustic li~uors, referred to herein as Bayer process liquor, is a critical step ~owards the economic recovery of aluminum value~. Bayer process operator~ optimize their precipitation methods so a~ to produce the greatest possible yield ~rom the Bayer proce~ liquors ~hile trylng to achieve a given crystal size di~tribution. It is de~irable in Most instances to obtain relatively large crystal ~iza since this is beneficial in subsequent proce~sing steps required ~o produce aluminum metal. Production is often limited by processing conditions under which the crystallization and precipitation is conducted. These proce~ing conditions vary from one plant to the next and include, but are not limited to, temperature profiles, seed charge, seed crystal surface area, liquor loading, liquor purity, and the like.
It is an extremely well known fact that organic impuritie~ in the Bayer process li~uors, which are normally derived from organics present in the Bauxite ore, can have a devasting effect on Bayer process crystallization practlce.
In addition to humate che~icals derived from the impure Bauxite ores, another primary organic contaminant is sodium oxalate, thought to be produced during the high temperature digestion of the raw material Bauxite ore in highly concentrated cau~tic solution~. Regardless of tha ~ource of sodium oxalate, it~ presence in Bayer procQss liquor3 i~ unde~irable for a number o~ rea~on~, as explained 36~ `~
in U.S> Patent No. 4,608,2370 Sodium oxalate often crystalize~ and co-precipitates from solution over esse~tially the same temperature profile~
as does the desired alumina trihydrate cry~tals. Fine oxalate particles act as sacondary nucleation site~ for alumina trihydrate, thereby increasing the total number of alumina crystals during the alumina trihydrate precipitation. This has an effect of causing a shift to smaller alumina trihydrate crystal size distribution and the production o~ very finely divided materials which for the most part are not wanted.
However, some of the smaller size alumina trihydrate ls needed, as will be explained. The general criterion is not to produce any more of the fine particle crystal than i5 needed for reseeding.
The oxalate crystal~, which are extremely Einely divided and have an extremely large surface area, adhere to the surfaces of growing alumina trihydrate agglomerates This adhesion of the oxalate crystalites int~rferes with both alumina trihydrate unit crystal growth and the agglomeration of alu~ina hydrate crystals. Occlusion of sodium oxalate crystalites within the growing alùmina trihydrate multicrystal al~o results in the weakening of the final crystal structure.
As noted above, this is very undesirable since it leads to the development of excessive amounts of extremely finely divided alumina trihydrate both during the precipitatior~ process as well as in the alumina trihydrate calcination processes which follow.
PRIOR ~RT: O~JECTIVES OF
THE INYENTION
The disclosure in U~S. Pa~ent No. 49608,237 i~ th~
prior art we addre~s. According to the disclo~ure in that , ~ 3~ 66530-4~9~
pa~en~ r the preoipitation of alumina hydrate crystals of coarse or ].arge si~e from a Bayer process qreen liquor is aided by employing certairl lakex polymers. Being in the latex form, these polymers are expensive to produce. Our object is to achieve yields of coarse alumina trihydra~e particles at least quantitatively equal to the achievement under Patent No.
4,608,237 but achieved merely hy blending a fat~y acid (or equivalent surfactant) and an oil, the two being soluble in one another, so that the treatment (a mere blend~ can be a matter of havlng the two liquids available at the plant and introducing them into the precipitation tank in-line with introduction of the green liquor charged into the precipitating tank. Another object of the invention is to present an economic alternative to the polymeric treatment of United States Patent No. 4,G08,237 by which to meet ~he general criterion of fine particle crystal size mentioned above.
THE INVENTION IN PRACTICE: EXAMPLE5 In one aspect, the invention provides a method o:E
reduciny the percent of small size alumina trihydrate crystals produced during crystallization of alumina trihydrate from a hot, caustic pregnant Bayer process liquor, thereby to inarease the yield of coarse crystals subsequently to be processed to yield aluminum, which comprises adding to the preqnant liquor, after red mud separation and prior to crystalliz.a~ion of alumina trihydrate, an effective amount of two mutually soluble components ~A) and IB), aomponent (A) being a surfactan~ which will diaperse component (B) in the pregnant li~uor and component (B) being an oil in which the surfactant is dissolved and having a boiling point above the temperature prevaiiing during alumina hydrate crystallization.
~,;, r~, ~ 3 :
63~
66s30-4~ss In another aspect, the invention provides a composi-tion for use in the method above, which composition comprises (A) a surfactant whi~h will not degrade to any~hing less than a tall oil equivalent in the presence of a hot strong caustic solution, together wi~h (B) an oil car~ier or solvent vehicle for the surfactant that has a boiling point safely above that of hot Bayer green liquor undergoing precipitation.
In the examples to $ollowr Bayer process pregnant or green liquors a~ different plants (Plant A, Plant B, and so on) were employed to determine if the invention was in any way limited by variaiions in precipitation parameters employed by different producers of aluminum, known only to them. These parameters include the nature of the ore, the amount of lmpurities whether organic or inorganic, caustic concentrations, and especially the condltions inside the precipitation tank which include the form and purity of the seed crystals tsmall particles of alumina trihydrate), the degree of agitation, time, temperature, and so on. While the details of the precipitation technlques at the various plants are not known, it is known that they do vary widely.
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We found the invention in practice i~ unaffected by different proprietary precipitation techni~ue~ involving process parameter~ unknown to us. Thi~ fact i~ of great significance because it establishes that r~egardless of the proprietary (unpublished) processing paramleter~ maintained inside the precipitating tank, the present invention for actual practice only requires blending and in-line injection of the two-constituent solution which composes the treatment.
The~e constituents are (A) a surfactant which will not degrade to anything less than a tall oil equivalent in the presence of a hot (up to 180-190F) strong caustic solution (e.g., 200 g/l alkalinity) together with ~B) an oil carrier or ~olvent vehicle for the atty acid. The oll need only be a ~olvent for the surfactant and have a boiling point safely above that oE hot Bayer green li~uor un~ergoing precipitation.
The preferred surfactant is tall oil fatty acid, but there are a host of equivalent~. Thus, the fatty acid is one having at least a saturated or unsaturated four carbon alkyl backbone, with or without one or more carboxylic acid, ester, ' anhydride or sulfate surfactant functional groups attached directly or by a succinic alkyl linkage. Advantageou~ly the fatty acid may contain at least an eight carbon backbone with at least one of the above functional groups attached.
The oil carrier may vary widely; the surfactants are ~5 oil soluble and there are many oils with a boiling point above say 200F~ Thu~ the oil may be a fatty alcoho}-ether-ester complex derived from Clo alcobol distillation; it may be one selected rom the paraffinic serie~, it may be an aromatic oil ~e.g. naphthenic oil) or it may be any mixture of the~e.
The oil specie~ that are possible, as equivalents, would ~ 2~i6~65 represent an almost endles~ list and our broad-based examples, though few in number, are intended to emphasize thi~ feature o the invention.
The mo~t preferred embodiment is a solution of tall oil fatty acid in a Clo alcohol distillation residue a~
the oil carrier, in the weight proportion of about 15:85, the dosage being about 20 mg/l. The next preferred embodiment is tall oil fatty acid (surfactant) in naphthenic oil ~s the oil carrier, in the weight proportion of 15:85 and the do~age being about 20 mg/l. The preferred oil carrier (fatty acid solvent) is the Clo alcohol distillation residue having a boiling point of about 250C (482~). It is light yellow to yellowish brown in color and has a specific gravity of 0.862, OH- number 90, SAP No. 50, weight percent acetic 0.07 and carbonyl 0.5. Its main source (and commercial description) is the distallatlon ~ottoms or resident from dlstilling a Clo alcohol. Chemically, it is 57-73 weight percent of primary branched chain Cl~-C22 alcohols (classed as fatty alcohols) and 29-41 weight percent of mixed long chain ester~
and ethers (Cl~-C33 ester; C18-C22 ether)-In all examples, the green or pregnant liquor (charge) employed for alumina trihydrate precipitation is the hot caustic solution obtained after elimination of the red mud in the Bayer process. It is not necessary to an understanding of thi9 invention to outline the whole Bayer process to those having skill in that art. The green liquor, after red mud separation, is a hott caustic filtrate, the commercial production green liquor containing the aluminum value~ a di~olved sodium aluminate. Thi~ liquor and recirculated fine ,, . _ _ . ......... .. .. . . . .. . . .
~2~ 3~;5 particle alumina trihydrate seeds are charged into a ~uitable precipitating tank or a series of connecting tanks. Here, th~
charge is cooled under agitation to stres~ the contents, cau~ing precipitation of alumina hydrate crystals on the seeds which constitute growth sites.
Complete elimination of the fine particle mate~ial (e.g. -32S mesh or smaller) is not wanted. There needs to be a remnant source oE seeds, following precipitation, for recirculation to serve the next generation of repeated growth in a continuous process.
In brief, the precipitation procass involves nucleation followed by (a) initial crystal growth and (b) agglomeration of those crystals into a coarse or ~andlike alumina trihydrate particle which will later be dried, and often calcined to obtain A1203 as the commercial product of value.
Also, in the examples to follow, the "oil carrier,"
unless otherwise noted, is the alcohol distill~tion residue identified above, and the "fatty acid" i~ tall oil. Percent~
are weight percent.
The object of Examples lA, lB and lC was to determine the response using different dosages of fatty acid/oil blend with different seed charges imposed on the green liquor of Plant A. Response in all examples is the percent reduction to a -325 mesh fraction of the aluminum hydrate cry~tal, equivalent to 44 or 45 micron~. The greater the reductivn, up to a limit, the better the performance in producin~ the large siza crystals for calcination. The "blank" in all examples i9 an undosed green liquor from the plant ~ite.
..~
.
~L2~
Exam~
Charge: Plant A green liquor; washed fine seed.
Treatment: 15% fatty acid ~refined tall oil) 85~ oil carrier Dose (m~tl) ~ Reduction Blank o.0 +5.1 +17.2 +31.4 100 +43.8
PRECIPITATION IN THE BAYER PROCESS
INTRODUCTION
_ This invention i~ concerned with treatment of a Bayer process green liquor rom which aluminum values are precipitated.
In the Bayer proce~s for Bauxite ore beneficiation, crystallization and precipitation of solubilized alumina trihydrate values from caustic li~uors, referred to herein as Bayer process liquor, is a critical step ~owards the economic recovery of aluminum value~. Bayer process operator~ optimize their precipitation methods so a~ to produce the greatest possible yield ~rom the Bayer proce~ liquors ~hile trylng to achieve a given crystal size di~tribution. It is de~irable in Most instances to obtain relatively large crystal ~iza since this is beneficial in subsequent proce~sing steps required ~o produce aluminum metal. Production is often limited by processing conditions under which the crystallization and precipitation is conducted. These proce~ing conditions vary from one plant to the next and include, but are not limited to, temperature profiles, seed charge, seed crystal surface area, liquor loading, liquor purity, and the like.
It is an extremely well known fact that organic impuritie~ in the Bayer process li~uors, which are normally derived from organics present in the Bauxite ore, can have a devasting effect on Bayer process crystallization practlce.
In addition to humate che~icals derived from the impure Bauxite ores, another primary organic contaminant is sodium oxalate, thought to be produced during the high temperature digestion of the raw material Bauxite ore in highly concentrated cau~tic solution~. Regardless of tha ~ource of sodium oxalate, it~ presence in Bayer procQss liquor3 i~ unde~irable for a number o~ rea~on~, as explained 36~ `~
in U.S> Patent No. 4,608,2370 Sodium oxalate often crystalize~ and co-precipitates from solution over esse~tially the same temperature profile~
as does the desired alumina trihydrate cry~tals. Fine oxalate particles act as sacondary nucleation site~ for alumina trihydrate, thereby increasing the total number of alumina crystals during the alumina trihydrate precipitation. This has an effect of causing a shift to smaller alumina trihydrate crystal size distribution and the production o~ very finely divided materials which for the most part are not wanted.
However, some of the smaller size alumina trihydrate ls needed, as will be explained. The general criterion is not to produce any more of the fine particle crystal than i5 needed for reseeding.
The oxalate crystal~, which are extremely Einely divided and have an extremely large surface area, adhere to the surfaces of growing alumina trihydrate agglomerates This adhesion of the oxalate crystalites int~rferes with both alumina trihydrate unit crystal growth and the agglomeration of alu~ina hydrate crystals. Occlusion of sodium oxalate crystalites within the growing alùmina trihydrate multicrystal al~o results in the weakening of the final crystal structure.
As noted above, this is very undesirable since it leads to the development of excessive amounts of extremely finely divided alumina trihydrate both during the precipitatior~ process as well as in the alumina trihydrate calcination processes which follow.
PRIOR ~RT: O~JECTIVES OF
THE INYENTION
The disclosure in U~S. Pa~ent No. 49608,237 i~ th~
prior art we addre~s. According to the disclo~ure in that , ~ 3~ 66530-4~9~
pa~en~ r the preoipitation of alumina hydrate crystals of coarse or ].arge si~e from a Bayer process qreen liquor is aided by employing certairl lakex polymers. Being in the latex form, these polymers are expensive to produce. Our object is to achieve yields of coarse alumina trihydra~e particles at least quantitatively equal to the achievement under Patent No.
4,608,237 but achieved merely hy blending a fat~y acid (or equivalent surfactant) and an oil, the two being soluble in one another, so that the treatment (a mere blend~ can be a matter of havlng the two liquids available at the plant and introducing them into the precipitation tank in-line with introduction of the green liquor charged into the precipitating tank. Another object of the invention is to present an economic alternative to the polymeric treatment of United States Patent No. 4,G08,237 by which to meet ~he general criterion of fine particle crystal size mentioned above.
THE INVENTION IN PRACTICE: EXAMPLE5 In one aspect, the invention provides a method o:E
reduciny the percent of small size alumina trihydrate crystals produced during crystallization of alumina trihydrate from a hot, caustic pregnant Bayer process liquor, thereby to inarease the yield of coarse crystals subsequently to be processed to yield aluminum, which comprises adding to the preqnant liquor, after red mud separation and prior to crystalliz.a~ion of alumina trihydrate, an effective amount of two mutually soluble components ~A) and IB), aomponent (A) being a surfactan~ which will diaperse component (B) in the pregnant li~uor and component (B) being an oil in which the surfactant is dissolved and having a boiling point above the temperature prevaiiing during alumina hydrate crystallization.
~,;, r~, ~ 3 :
63~
66s30-4~ss In another aspect, the invention provides a composi-tion for use in the method above, which composition comprises (A) a surfactant whi~h will not degrade to any~hing less than a tall oil equivalent in the presence of a hot strong caustic solution, together wi~h (B) an oil car~ier or solvent vehicle for the surfactant that has a boiling point safely above that of hot Bayer green liquor undergoing precipitation.
In the examples to $ollowr Bayer process pregnant or green liquors a~ different plants (Plant A, Plant B, and so on) were employed to determine if the invention was in any way limited by variaiions in precipitation parameters employed by different producers of aluminum, known only to them. These parameters include the nature of the ore, the amount of lmpurities whether organic or inorganic, caustic concentrations, and especially the condltions inside the precipitation tank which include the form and purity of the seed crystals tsmall particles of alumina trihydrate), the degree of agitation, time, temperature, and so on. While the details of the precipitation technlques at the various plants are not known, it is known that they do vary widely.
:: :
:
:~ :
;
i .
~ 3a ,: ~
.~
We found the invention in practice i~ unaffected by different proprietary precipitation techni~ue~ involving process parameter~ unknown to us. Thi~ fact i~ of great significance because it establishes that r~egardless of the proprietary (unpublished) processing paramleter~ maintained inside the precipitating tank, the present invention for actual practice only requires blending and in-line injection of the two-constituent solution which composes the treatment.
The~e constituents are (A) a surfactant which will not degrade to anything less than a tall oil equivalent in the presence of a hot (up to 180-190F) strong caustic solution (e.g., 200 g/l alkalinity) together with ~B) an oil carrier or ~olvent vehicle for the atty acid. The oll need only be a ~olvent for the surfactant and have a boiling point safely above that oE hot Bayer green li~uor un~ergoing precipitation.
The preferred surfactant is tall oil fatty acid, but there are a host of equivalent~. Thus, the fatty acid is one having at least a saturated or unsaturated four carbon alkyl backbone, with or without one or more carboxylic acid, ester, ' anhydride or sulfate surfactant functional groups attached directly or by a succinic alkyl linkage. Advantageou~ly the fatty acid may contain at least an eight carbon backbone with at least one of the above functional groups attached.
The oil carrier may vary widely; the surfactants are ~5 oil soluble and there are many oils with a boiling point above say 200F~ Thu~ the oil may be a fatty alcoho}-ether-ester complex derived from Clo alcobol distillation; it may be one selected rom the paraffinic serie~, it may be an aromatic oil ~e.g. naphthenic oil) or it may be any mixture of the~e.
The oil specie~ that are possible, as equivalents, would ~ 2~i6~65 represent an almost endles~ list and our broad-based examples, though few in number, are intended to emphasize thi~ feature o the invention.
The mo~t preferred embodiment is a solution of tall oil fatty acid in a Clo alcohol distillation residue a~
the oil carrier, in the weight proportion of about 15:85, the dosage being about 20 mg/l. The next preferred embodiment is tall oil fatty acid (surfactant) in naphthenic oil ~s the oil carrier, in the weight proportion of 15:85 and the do~age being about 20 mg/l. The preferred oil carrier (fatty acid solvent) is the Clo alcohol distillation residue having a boiling point of about 250C (482~). It is light yellow to yellowish brown in color and has a specific gravity of 0.862, OH- number 90, SAP No. 50, weight percent acetic 0.07 and carbonyl 0.5. Its main source (and commercial description) is the distallatlon ~ottoms or resident from dlstilling a Clo alcohol. Chemically, it is 57-73 weight percent of primary branched chain Cl~-C22 alcohols (classed as fatty alcohols) and 29-41 weight percent of mixed long chain ester~
and ethers (Cl~-C33 ester; C18-C22 ether)-In all examples, the green or pregnant liquor (charge) employed for alumina trihydrate precipitation is the hot caustic solution obtained after elimination of the red mud in the Bayer process. It is not necessary to an understanding of thi9 invention to outline the whole Bayer process to those having skill in that art. The green liquor, after red mud separation, is a hott caustic filtrate, the commercial production green liquor containing the aluminum value~ a di~olved sodium aluminate. Thi~ liquor and recirculated fine ,, . _ _ . ......... .. .. . . . .. . . .
~2~ 3~;5 particle alumina trihydrate seeds are charged into a ~uitable precipitating tank or a series of connecting tanks. Here, th~
charge is cooled under agitation to stres~ the contents, cau~ing precipitation of alumina hydrate crystals on the seeds which constitute growth sites.
Complete elimination of the fine particle mate~ial (e.g. -32S mesh or smaller) is not wanted. There needs to be a remnant source oE seeds, following precipitation, for recirculation to serve the next generation of repeated growth in a continuous process.
In brief, the precipitation procass involves nucleation followed by (a) initial crystal growth and (b) agglomeration of those crystals into a coarse or ~andlike alumina trihydrate particle which will later be dried, and often calcined to obtain A1203 as the commercial product of value.
Also, in the examples to follow, the "oil carrier,"
unless otherwise noted, is the alcohol distill~tion residue identified above, and the "fatty acid" i~ tall oil. Percent~
are weight percent.
The object of Examples lA, lB and lC was to determine the response using different dosages of fatty acid/oil blend with different seed charges imposed on the green liquor of Plant A. Response in all examples is the percent reduction to a -325 mesh fraction of the aluminum hydrate cry~tal, equivalent to 44 or 45 micron~. The greater the reductivn, up to a limit, the better the performance in producin~ the large siza crystals for calcination. The "blank" in all examples i9 an undosed green liquor from the plant ~ite.
..~
.
~L2~
Exam~
Charge: Plant A green liquor; washed fine seed.
Treatment: 15% fatty acid ~refined tall oil) 85~ oil carrier Dose (m~tl) ~ Reduction Blank o.0 +5.1 +17.2 +31.4 100 +43.8
2~0 +63.0 400 ~55.~
Example lB
Charge: Plant A green liquor Unwashed fine seed Treatment: 15% atty acid ~refined tall oil) 85% oil carxier Dose (mg/l) ~ Reduction _ Blank 0,5 ~15.7 ~31.
100 +50~0 Comparing lA and lB it is ~een that there is little di~ference in the effect o the treatment whether or not the (recirculated~ fine seed is washed for more purity.
Example lC
Charge: Plant A
Coarse seed (washed) Treatment: 15~ Fatty acid ~tall oil, ref.ined) 85~ oil carrier % Reduction Blank o.o 5~ ~66~7 100 +66.7 Example lC shows a coarser ~eed particl~ has no adverse effect on the present treatment; compare Example lA, "fine seed~"
:,, . . . ~
i3~
Example lD
Charge: Plant B
Fine 3eed ~washed) Treatment: 15~ Fatty acid (unrefined tall oil) 85% Oil carrier Dose (mg/l) % Reduction Blank 0.0 ~29.0 ~24~0 +26.0 Example lE
Charge: Plant C
~ine ~eed (unwashed) Treatment: 15% Fatty acid ~unrefined tall oil) 85~ Mineral seal oil ~carrier~
Dose ~mg/l) % Reduction Blank 0.0 ~30.0 Examples lD and lE verify that beneficial re~ults in percent reduction are achieved with different plant proce~ses for precipitation, different seed charges and differe~t tall oil purity.
In Example lE, the oil carrier i~ paraffinic, ~b.p 150C or higher), performing every bit as well as the Clo alcohol distillation residue.
The object of the following example (2A) was to determine the benefit, if any, using different ratios of fatty acid:and oil carrier, compared to the fatty acid employed by it~elf as a treatment. The fatty acid in thiq example wa~
:: unrefined ta~l oil.
~ ~ :
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Example_2A
Charge: Plant B
Fine seed (wa~hed) Treatment Dose (mg/l~ ~ Reduction slank o o Fatty acid in oil carrier 15% 50 ~23 30% 50 +37 45~ 50 +35 60~ 50 +~1 75~ S~ +18 Fatty acid alone 100~ 5~ -25 From this example, a 30-45 weight percent ratio of ~atty acid in oil i~ optimum. Negative result~ are achieved without the oil carrier ~or the fatty acid.
The object of the ollowing example is to determine if beneficial results are obtained regardle~s of the order in which the component~ are added. The fatty acid was refined tall oil.
Example 3A
Charge: Plant A
Fine seed ~washed) Treatment Dose ~mg/1) % Reduction Blank 0 0 Yatty acid ~15~) in o11 carrier 100 +33.6 Fatty acid followed by oil carrier 15+85 ~43.4 Oil carrier followed-by fatty acid 85+15 +38.9 Desirable re~ults were obtained regardless o~ the order of addition.
The following two example~ were undertake~ to _g_ - . , , : .. - ,
Example lB
Charge: Plant A green liquor Unwashed fine seed Treatment: 15% atty acid ~refined tall oil) 85% oil carxier Dose (mg/l) ~ Reduction _ Blank 0,5 ~15.7 ~31.
100 +50~0 Comparing lA and lB it is ~een that there is little di~ference in the effect o the treatment whether or not the (recirculated~ fine seed is washed for more purity.
Example lC
Charge: Plant A
Coarse seed (washed) Treatment: 15~ Fatty acid ~tall oil, ref.ined) 85~ oil carrier % Reduction Blank o.o 5~ ~66~7 100 +66.7 Example lC shows a coarser ~eed particl~ has no adverse effect on the present treatment; compare Example lA, "fine seed~"
:,, . . . ~
i3~
Example lD
Charge: Plant B
Fine 3eed ~washed) Treatment: 15~ Fatty acid (unrefined tall oil) 85% Oil carrier Dose (mg/l) % Reduction Blank 0.0 ~29.0 ~24~0 +26.0 Example lE
Charge: Plant C
~ine ~eed (unwashed) Treatment: 15% Fatty acid ~unrefined tall oil) 85~ Mineral seal oil ~carrier~
Dose ~mg/l) % Reduction Blank 0.0 ~30.0 Examples lD and lE verify that beneficial re~ults in percent reduction are achieved with different plant proce~ses for precipitation, different seed charges and differe~t tall oil purity.
In Example lE, the oil carrier i~ paraffinic, ~b.p 150C or higher), performing every bit as well as the Clo alcohol distillation residue.
The object of the following example (2A) was to determine the benefit, if any, using different ratios of fatty acid:and oil carrier, compared to the fatty acid employed by it~elf as a treatment. The fatty acid in thiq example wa~
:: unrefined ta~l oil.
~ ~ :
:
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Example_2A
Charge: Plant B
Fine seed (wa~hed) Treatment Dose (mg/l~ ~ Reduction slank o o Fatty acid in oil carrier 15% 50 ~23 30% 50 +37 45~ 50 +35 60~ 50 +~1 75~ S~ +18 Fatty acid alone 100~ 5~ -25 From this example, a 30-45 weight percent ratio of ~atty acid in oil i~ optimum. Negative result~ are achieved without the oil carrier ~or the fatty acid.
The object of the ollowing example is to determine if beneficial results are obtained regardle~s of the order in which the component~ are added. The fatty acid was refined tall oil.
Example 3A
Charge: Plant A
Fine seed ~washed) Treatment Dose ~mg/1) % Reduction Blank 0 0 Yatty acid ~15~) in o11 carrier 100 +33.6 Fatty acid followed by oil carrier 15+85 ~43.4 Oil carrier followed-by fatty acid 85+15 +38.9 Desirable re~ults were obtained regardless o~ the order of addition.
The following two example~ were undertake~ to _g_ - . , , : .. - ,
3~iS
determine whether a fatty acid (refined tall oil) dis~olved in an oil carrier performs better than an oiI carrier aloneO
Also, whether there would be an appreciable difference between a petroleum-derived (paraffin series) oil carrier and an aromatic oil employed as the carrier. In thes~ two examples ~4A, 4Bj the fatty acid was xefined tall ~
.. .. . .... ...
3~
~Xample 4A
Charge: Plant ~
Fine seed (washed) Treatment ; Dose (m~/l) % Reduction Blank 0 0 15% fatty acid in oil carrier 100 +30.0 oil carrier only 85 +14.1 15% fatty acid in high aromatic oil(l) 100 +24.3 High aromatic oil(l) 85 0 15~ fatty acid in oil ~15% aromatic oil)(2) 100 +22.4 Oil (~15~ aromatic oil) alone(2) 85 + 4.4 15% fatty acid in low aromatic oil(3) 100 +34.6 Low aromatic oil alone 85 ~15.1 ~1) Exxon*Aromatic 150 ~98%) (2) VM~P*Naptha (3) Exxon low odor paraffinic oil (4~ axomatic) ~xample 4B
Chargë: Plant B
Fine seed (washed) Treatment Does (m~/l) % Reductlon Blank 0 0 : 15~ fatty acid in naphthenic oil 5~ ~36 15% fatty acid in paraffinic oil 50 -~27 15% fatty acid in oil carrier 50 ~ +28 :~ 15~ fatty acid in mineral oil 50 +25 The data of these two examples show inferior performance~when an oil (whether alcoholic,aliphatic or : aromatic) is used alone, without any ~atty acid, but the *Trade Mark ~ ~ ~ ~ ~3 rank of the oil carrier (aliphatic, alcoholic, aromatic or mixed~ is immaterial.
Example 5A, which follow~, was to determine any synergistic effect of the fatty acid/oil blend compared to each separate component by itself.
Example 5A
Charge: Plant C
Fine seed ~unwashed~
% Reduction Treatment Dose ~mg/l) in -325 Mesh lo Blank o 0 15~ fatty acid in mi~eral seal oil 50 +30 100% mineral seal oil 50 0 100% fatty acld 50 -41 The tall oil Eatty acid by itsel give~ in~erior perEormance compared to the paraffinic oll by itself ~whlch gives nothing more than a nul re~ult, the ~ame a~ the ~lank) but as will be shown by Examples 6A and 6B many different species of fatty acids are effective when combined with an oil carrier.
Example ~A
Charge: Plant A
Fine seed ~wa~hed) % Reduction Treatment Dose ~m~/l) in -325 _Mesh ~ ~Blank o 0 15~ refined tall : oil in oil carrier 100 +24.2 15~ unrefined tall oil in oil carrier 100 + 7.0 : :
, ~z~3~;
.
Charges Plant A
Fine seed (wa~hed) ~ Reduction Treatment Dose (m~/l) in -325 Mesh 15~ fatty acid (low ro~in) in an oil carrier 50 ~29 15% fatty acid (high rosin) in an oil carrier 50 +25 15% fatty acid ~high pitch) in an oil carrier 50 ~24 15% mixture of oleic and stearic acids in an oil carrier 50 ~31 15% ~tearic acid in an oil carrier 50 ~3 15% oleic acid in an oil carrier 50 +20 15% n-octenylsuccinic anhydride in an oil carrier 50 ~12 15~
n-dodecenylsuccinic anhydride in an oil carrier 50 ~16 15~ isomerized dodecenylsuccinic anhydride in an oil carrier 50 ~1~
In Example 6B, the fatty acids of the fir~t three compositions tested were respectively a tall oil with low rosin content, one with high rosin content and one with a high content of pitch, none of which made any appreciable or noteworthy difference. In this example ~6B) all the acids are eguated to the fatty acid cla~ because the alkenyl succinic anhydrides hydrolyze in the Bayer pregnant liquor to alkenyl (dicarboxylic) fatty acid.
`:. ' ", ., "
The following three examples demonstrate that surfactants other than a fatty acid may be successfully employed as an equiYalent.
~xam~le 7A
Charge: Plant A
Fine seed (washed) Treatment Dose (mg/l) ~ Reductlon Blank o o 15~ sodium lauryl sulfate in oil carrier 100 +26.5 15~ complex (1) phosphate ester in oil carrier 100 +31.4 C12 linear alkyl -amino butyric acid in oil carrier (2) 100 +29.4 (1) GAFAC BH-650 (GAF Company) (2) this carboxy acid is also known as betaine .
Example 7B
Charge: Plant B
Fine seed (washed) Treatment Dose tmg/l) ~ Reduction Blank o o Sulfonated tall oil in oil carrier 50 ~17 -methacrylic acid stearylmethacrylate .
copolymer in oil carrier ~ 50 : +18 15~ fatty : amide tl) in : mineral seal oil: 50 ~L4 : : tl) amide o~ refined tall oil, which degrades to tall oil in the green oil Bayer liquor, trade mark.
Charge: Plant C
Fine ~eed ~wa~hed) Do~e % Reduction _oduct ~m~ in -325 Me~h Blank o o 15% fatty amide~ 0 ~22 in mineral s~al oil ~1) amide of refin2d tall oil which degrades to tall oil in the green Bayer liquor Example 8A
This example was to determina whether the fatty acid/oil treatment o the present invention would be eective when coupled with a Bayer process liquor at Plant X having no appreciable, if any, oxalate in the green liquor. The treatment remained eEEective, that is, the absence of the oxalate made no difference:
,:
:
. ; . : - .
i;3~
Wt.~ Dose (m~/l) % Reductisn , Tall Oil Amide 50 22 Mineral Seal Oil Refined Tall Oil 50 30 8S Minexal Seal Oil Crude Tall Oil Amide 50 30 Oil Carrier 100 Refined Tall Oil 50 0 10G Mineral Seal Oil 50 0 Blank __ 0 The examples are intended to demon3trate that the u~eful surfactants cover a wide range of chemical variants with or without attached functional groups which may contribute more surface activity to the surfactant compound.
Thereore, manv equivalents may be employed to supplant tall oil as long a~ the surfactant will disperse the oll in the hot caustLc Bayer green liquor. The oil, as noted, is a hlgh boiling point solvent for the surfactant and again there is a wide range of equivalents for the preferred species which i9 the distillation bottoms rom distilling a Clo alcohol by oxy processing. Hence while we have set forth a preferred embodiment o the invention it i~ to be under~tood this is capable o~ variation and ~odificatlon.
~ ' .
.
3~
It will be seen from the foregoing that unde~ thepr2sent inven~ion practiced with a hot caust~c Bayer process green liquor, the treatment to shift or bias precipitation of alumina trihydrate crystals toward the coarser size is a surfactant combined with an oil. The oil itself is a solvent for the surfactant, with a boiling point well above the temperature prevailing during precipitation, while the surfactant in turn is a dispersant or emulsifier for the oil.
determine whether a fatty acid (refined tall oil) dis~olved in an oil carrier performs better than an oiI carrier aloneO
Also, whether there would be an appreciable difference between a petroleum-derived (paraffin series) oil carrier and an aromatic oil employed as the carrier. In thes~ two examples ~4A, 4Bj the fatty acid was xefined tall ~
.. .. . .... ...
3~
~Xample 4A
Charge: Plant ~
Fine seed (washed) Treatment ; Dose (m~/l) % Reduction Blank 0 0 15% fatty acid in oil carrier 100 +30.0 oil carrier only 85 +14.1 15% fatty acid in high aromatic oil(l) 100 +24.3 High aromatic oil(l) 85 0 15~ fatty acid in oil ~15% aromatic oil)(2) 100 +22.4 Oil (~15~ aromatic oil) alone(2) 85 + 4.4 15% fatty acid in low aromatic oil(3) 100 +34.6 Low aromatic oil alone 85 ~15.1 ~1) Exxon*Aromatic 150 ~98%) (2) VM~P*Naptha (3) Exxon low odor paraffinic oil (4~ axomatic) ~xample 4B
Chargë: Plant B
Fine seed (washed) Treatment Does (m~/l) % Reductlon Blank 0 0 : 15~ fatty acid in naphthenic oil 5~ ~36 15% fatty acid in paraffinic oil 50 -~27 15% fatty acid in oil carrier 50 ~ +28 :~ 15~ fatty acid in mineral oil 50 +25 The data of these two examples show inferior performance~when an oil (whether alcoholic,aliphatic or : aromatic) is used alone, without any ~atty acid, but the *Trade Mark ~ ~ ~ ~ ~3 rank of the oil carrier (aliphatic, alcoholic, aromatic or mixed~ is immaterial.
Example 5A, which follow~, was to determine any synergistic effect of the fatty acid/oil blend compared to each separate component by itself.
Example 5A
Charge: Plant C
Fine seed ~unwashed~
% Reduction Treatment Dose ~mg/l) in -325 Mesh lo Blank o 0 15~ fatty acid in mi~eral seal oil 50 +30 100% mineral seal oil 50 0 100% fatty acld 50 -41 The tall oil Eatty acid by itsel give~ in~erior perEormance compared to the paraffinic oll by itself ~whlch gives nothing more than a nul re~ult, the ~ame a~ the ~lank) but as will be shown by Examples 6A and 6B many different species of fatty acids are effective when combined with an oil carrier.
Example ~A
Charge: Plant A
Fine seed ~wa~hed) % Reduction Treatment Dose ~m~/l) in -325 _Mesh ~ ~Blank o 0 15~ refined tall : oil in oil carrier 100 +24.2 15~ unrefined tall oil in oil carrier 100 + 7.0 : :
, ~z~3~;
.
Charges Plant A
Fine seed (wa~hed) ~ Reduction Treatment Dose (m~/l) in -325 Mesh 15~ fatty acid (low ro~in) in an oil carrier 50 ~29 15% fatty acid (high rosin) in an oil carrier 50 +25 15% fatty acid ~high pitch) in an oil carrier 50 ~24 15% mixture of oleic and stearic acids in an oil carrier 50 ~31 15% ~tearic acid in an oil carrier 50 ~3 15% oleic acid in an oil carrier 50 +20 15% n-octenylsuccinic anhydride in an oil carrier 50 ~12 15~
n-dodecenylsuccinic anhydride in an oil carrier 50 ~16 15~ isomerized dodecenylsuccinic anhydride in an oil carrier 50 ~1~
In Example 6B, the fatty acids of the fir~t three compositions tested were respectively a tall oil with low rosin content, one with high rosin content and one with a high content of pitch, none of which made any appreciable or noteworthy difference. In this example ~6B) all the acids are eguated to the fatty acid cla~ because the alkenyl succinic anhydrides hydrolyze in the Bayer pregnant liquor to alkenyl (dicarboxylic) fatty acid.
`:. ' ", ., "
The following three examples demonstrate that surfactants other than a fatty acid may be successfully employed as an equiYalent.
~xam~le 7A
Charge: Plant A
Fine seed (washed) Treatment Dose (mg/l) ~ Reductlon Blank o o 15~ sodium lauryl sulfate in oil carrier 100 +26.5 15~ complex (1) phosphate ester in oil carrier 100 +31.4 C12 linear alkyl -amino butyric acid in oil carrier (2) 100 +29.4 (1) GAFAC BH-650 (GAF Company) (2) this carboxy acid is also known as betaine .
Example 7B
Charge: Plant B
Fine seed (washed) Treatment Dose tmg/l) ~ Reduction Blank o o Sulfonated tall oil in oil carrier 50 ~17 -methacrylic acid stearylmethacrylate .
copolymer in oil carrier ~ 50 : +18 15~ fatty : amide tl) in : mineral seal oil: 50 ~L4 : : tl) amide o~ refined tall oil, which degrades to tall oil in the green oil Bayer liquor, trade mark.
Charge: Plant C
Fine ~eed ~wa~hed) Do~e % Reduction _oduct ~m~ in -325 Me~h Blank o o 15% fatty amide~ 0 ~22 in mineral s~al oil ~1) amide of refin2d tall oil which degrades to tall oil in the green Bayer liquor Example 8A
This example was to determina whether the fatty acid/oil treatment o the present invention would be eective when coupled with a Bayer process liquor at Plant X having no appreciable, if any, oxalate in the green liquor. The treatment remained eEEective, that is, the absence of the oxalate made no difference:
,:
:
. ; . : - .
i;3~
Wt.~ Dose (m~/l) % Reductisn , Tall Oil Amide 50 22 Mineral Seal Oil Refined Tall Oil 50 30 8S Minexal Seal Oil Crude Tall Oil Amide 50 30 Oil Carrier 100 Refined Tall Oil 50 0 10G Mineral Seal Oil 50 0 Blank __ 0 The examples are intended to demon3trate that the u~eful surfactants cover a wide range of chemical variants with or without attached functional groups which may contribute more surface activity to the surfactant compound.
Thereore, manv equivalents may be employed to supplant tall oil as long a~ the surfactant will disperse the oll in the hot caustLc Bayer green liquor. The oil, as noted, is a hlgh boiling point solvent for the surfactant and again there is a wide range of equivalents for the preferred species which i9 the distillation bottoms rom distilling a Clo alcohol by oxy processing. Hence while we have set forth a preferred embodiment o the invention it i~ to be under~tood this is capable o~ variation and ~odificatlon.
~ ' .
.
3~
It will be seen from the foregoing that unde~ thepr2sent inven~ion practiced with a hot caust~c Bayer process green liquor, the treatment to shift or bias precipitation of alumina trihydrate crystals toward the coarser size is a surfactant combined with an oil. The oil itself is a solvent for the surfactant, with a boiling point well above the temperature prevailing during precipitation, while the surfactant in turn is a dispersant or emulsifier for the oil.
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of reducing the percent of small size alumina trihydrate crystals produced during crystallization of alumina trihydrate from a hot, caustic pregnant Bayer process liquor, thereby to increase the yield of coarse crystals subsequently to be processed to yield aluminum, which comprises adding to the pregnant liquor, after red mud separation and prior to crystallization of alumina trihydrate, an effective amount of two mutually soluble components (A) and (B), component (A) being a surfactant which will disperse component (B) in the pregnant liquor and component (B) being an oil in which the surfactant is dissolved and having a boiling point above the temperature prevailing during alumina hydrate crystallization.
2. A method according to claim 1 in which component (B) is an oil selected from the group consisting of:
(1) paraffinic;
(2) naphthenic;
(3) mixed paraffinic and aromatic;
(4) the residue of C10 alcohol distillation.
(1) paraffinic;
(2) naphthenic;
(3) mixed paraffinic and aromatic;
(4) the residue of C10 alcohol distillation.
3. A method according to claim 1 in which the surfactant is a fatty acid that has at least a saturated or unsaturated four carbon alkyl backbone, with one or more carboxylic acid, ester, anhydride or sulfate surfactant functional groups attached directly or by a succinic alkyl linkage.
4. A method according to claim 3 in which the fatty acid has an at least eight carbon atom backbone.
5. A method according to claim 1, 2 or 3 in which the ratio of the amount of component (A) to component (B) is in the range 15:85 to 45:55.
6. A method according to claim 1 in which the surfactant is a tall oil fatty acid.
7. A method according to claim 6 in which the oil is the residue of C10 alcohol distillation.
8. A method according to claim 6 in which the oil is a naphthenic oil.
9. A method according to claim 7 wherein the ratio of tall oil to residue is about 15:85 by weight.
10. A method according to claim 9 wherein the mixture of tall oil and residue is added to the Bayer liquor at a dosage of about 20 mg/1.
11. A method according to claim 8 wherein the ratio of tall oil to naphthenic oil is about 15:85 by weight.
12. A method according to claim 11 wherein the mixture of tall oil and naphthenic oil is added to the Bayer liquor at a dosage of about 20 mg/1.
13. A method according to claim 1 wherein the components (A) and (B) are added separately in the order (A), (B).
14. A method according to claim 1 wherein the components (A) and (B) are added separately in the order (B), (A).
15. A method according to claim 1 wherein the components (A) and (B) are added simultaneously.
16. A method according to claim 1 wherein the components (A) and (B) are added mixed together.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36,389 | 1987-04-09 | ||
| US07/036,389 US4737352A (en) | 1987-04-09 | 1987-04-09 | Use of surfactants in alumina precipitation in the bayer process |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000615584A Division CA1275889C (en) | 1987-04-09 | 1989-12-27 | Surfactant compositions in alumina precipitation in the bayer process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1266365A true CA1266365A (en) | 1990-03-06 |
Family
ID=21888347
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000563608A Expired - Fee Related CA1266365A (en) | 1987-04-09 | 1988-04-08 | Use of surfactants in alumina precipitation in the bayer process |
| CA000615584A Expired - Lifetime CA1275889C (en) | 1987-04-09 | 1989-12-27 | Surfactant compositions in alumina precipitation in the bayer process |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000615584A Expired - Lifetime CA1275889C (en) | 1987-04-09 | 1989-12-27 | Surfactant compositions in alumina precipitation in the bayer process |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4737352A (en) |
| EP (1) | EP0286034B1 (en) |
| JP (1) | JPS6414111A (en) |
| CN (1) | CN1016866B (en) |
| AU (1) | AU593987B2 (en) |
| BR (1) | BR8801621A (en) |
| CA (2) | CA1266365A (en) |
| DE (2) | DE286034T1 (en) |
| ES (1) | ES2010966B3 (en) |
| HU (1) | HU202789B (en) |
| YU (1) | YU46453B (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE97392T1 (en) * | 1988-06-30 | 1993-12-15 | Ind Minerals Res & Dev | DEWATERING OF ALUMINUM TRIHYDRATE AND DEWATERING AGENT. |
| US5106599A (en) * | 1990-02-06 | 1992-04-21 | Nalco Chemical Company | Alumina crystal growth additive |
| DE4039053A1 (en) * | 1990-12-07 | 1992-06-11 | Henkel Kgaa | POLYGLYCERINE IN THE BAYER PROCESS |
| DE69308777T2 (en) | 1992-12-14 | 1997-07-31 | Nalco Chemical Co | Change of trihydrate crystals in the Bayer process |
| CA2126914A1 (en) * | 1993-06-30 | 1994-12-31 | Gillain Mary Moody | Production of alumina |
| JP2784882B2 (en) * | 1994-04-28 | 1998-08-06 | 第一工業製薬株式会社 | Process for producing powdery high melting point 2,2-bis [4 '-(2 ", 3" -dibromopropoxy) -3', 5'-dibromophenyl] propane |
| US5607598A (en) * | 1995-07-14 | 1997-03-04 | Ormet Corporation | Treatment and disposal of red mud generated in the Bayer Process |
| US6293973B1 (en) | 1996-10-11 | 2001-09-25 | Nalco Chemical Company | Method of controlling oxalate precipitation in bayer process liquor |
| US5902560A (en) * | 1997-08-28 | 1999-05-11 | Nalco Chemical Company | Method for inhibiting precipitation of sodium oxalate in a Bayer process liquor |
| GB9800855D0 (en) | 1998-01-15 | 1998-03-11 | Allied Colloids Ltd | Production of alumina |
| BR9913933A (en) | 1998-09-25 | 2002-02-19 | Worsley Alumina Pty Ltd | Improved bayer causticization |
| AU2004201629B2 (en) * | 1998-09-25 | 2006-07-13 | South32 Worsley Alumina Pty Ltd | Improved bayer causticisation |
| DE10113294A1 (en) * | 2001-03-16 | 2002-09-19 | Stockhausen Chem Fab Gmbh | Formation of aluminum oxide hydrate crystals from caustic mother liquors |
| US8971913B2 (en) * | 2003-06-27 | 2015-03-03 | Qualcomm Incorporated | Method and apparatus for wireless network hybrid positioning |
| US7976820B2 (en) * | 2005-06-23 | 2011-07-12 | Nalco Company | Composition and method for improved aluminum hydroxide production |
| US7955589B2 (en) | 2005-06-23 | 2011-06-07 | Nalco Company | Composition and method for improved aluminum hydroxide production |
| US7976821B2 (en) * | 2005-06-23 | 2011-07-12 | Nalco Company | Composition and method for improved aluminum hydroxide production |
| CN100411989C (en) * | 2006-01-23 | 2008-08-20 | 中国铝业股份有限公司 | Method for dissolving out gibbsite |
| US8628737B2 (en) * | 2006-11-09 | 2014-01-14 | Nalco Company | Transfer of slurry in a bayer process |
| US7771681B2 (en) | 2006-12-29 | 2010-08-10 | Nalco Company | Method for improved aluminum hydroxide production |
| US8282689B2 (en) * | 2009-07-01 | 2012-10-09 | Nalco Company | Composition and method for enhancing the production of crystal agglomerates from a precipitation liquor |
| US8298508B2 (en) | 2010-08-09 | 2012-10-30 | Nalco Company | Recovery of alumina trihydrate during the bayer process using cross-linked polysaccharides |
| US9199855B2 (en) | 2010-08-09 | 2015-12-01 | Nalco Company | Chemical treatment to improve red mud separation and washing in the bayer process |
| US9102995B2 (en) | 2010-08-09 | 2015-08-11 | Nalco Company | Cross-linked ethylsulfonated dihydroxypropyl cellulose |
| JP2016517385A (en) * | 2013-03-13 | 2016-06-16 | ナルコ カンパニー | Cross-linked ethyl sulfonated dihydroxypropyl cellulose |
| US8920768B2 (en) | 2013-03-14 | 2014-12-30 | Ecolab Usa Inc. | Crystallization aids for bayer aluminum hydroxide |
| US9896366B2 (en) | 2014-02-26 | 2018-02-20 | Ecolab Usa Inc. | Alternative additives to enhance slurry dewatering |
| US9592456B2 (en) * | 2015-02-11 | 2017-03-14 | Ecolab Usa Inc. | Methods for enhancing production of aluminum hydroxide in an aluminum hydroxide production process |
| EA033081B1 (en) | 2015-03-11 | 2019-08-30 | Сайтек Индастриз, Инк. | Oil-free crystal growth modifiers for alumina recovery |
| US10427950B2 (en) | 2015-12-04 | 2019-10-01 | Ecolab Usa Inc. | Recovery of mining processing product using boronic acid-containing polymers |
| US10259721B2 (en) * | 2016-09-09 | 2019-04-16 | Cytec Industries Inc. | Oil free crystal growth modifiers for the bayer process |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE636707C (en) | 1933-07-26 | 1936-10-15 | Chemische Fabriken Akt Ges Gam | Process for the precipitation of alumina hydrate from alkali aluminate solutions |
| US2440378A (en) * | 1946-09-13 | 1948-04-27 | Aluminum Co Of America | Treatment of sodium aluminate solutions |
| ZA713178B (en) * | 1971-05-17 | 1972-01-26 | Nalco Chemical Co | Continuous process for preparing extruded alumina bodies |
| US4578255A (en) * | 1984-12-27 | 1986-03-25 | Kaiser Aluminum Chemical Corporation | Purification of Bayer process liquors |
| US4608237A (en) * | 1985-04-24 | 1986-08-26 | Nalco Chemical Company | Use of polymers in alumina precipitation in the Bayer process of bauxite beneficiation |
-
1987
- 1987-04-09 US US07/036,389 patent/US4737352A/en not_active Expired - Lifetime
-
1988
- 1988-03-30 AU AU14017/88A patent/AU593987B2/en not_active Expired
- 1988-03-31 DE DE198888105315T patent/DE286034T1/en active Pending
- 1988-03-31 DE DE8888105315T patent/DE3862052D1/en not_active Expired - Fee Related
- 1988-03-31 EP EP88105315A patent/EP0286034B1/en not_active Expired - Lifetime
- 1988-03-31 ES ES88105315T patent/ES2010966B3/en not_active Expired - Lifetime
- 1988-04-06 BR BR8801621A patent/BR8801621A/en unknown
- 1988-04-08 HU HU881789A patent/HU202789B/en not_active IP Right Cessation
- 1988-04-08 YU YU71088A patent/YU46453B/en unknown
- 1988-04-08 CA CA000563608A patent/CA1266365A/en not_active Expired - Fee Related
- 1988-04-08 CN CN88101926A patent/CN1016866B/en not_active Expired
- 1988-04-09 JP JP63086295A patent/JPS6414111A/en active Pending
-
1989
- 1989-12-27 CA CA000615584A patent/CA1275889C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU593987B2 (en) | 1990-02-22 |
| YU71088A (en) | 1990-02-28 |
| HU202789B (en) | 1991-04-29 |
| DE286034T1 (en) | 1989-12-28 |
| ES2010966B3 (en) | 1991-10-16 |
| AU1401788A (en) | 1988-10-13 |
| DE3862052D1 (en) | 1991-04-25 |
| CN1016866B (en) | 1992-06-03 |
| US4737352A (en) | 1988-04-12 |
| ES2010966A4 (en) | 1989-12-16 |
| BR8801621A (en) | 1988-11-08 |
| YU46453B (en) | 1993-10-20 |
| CN88101926A (en) | 1988-10-26 |
| CA1275889C (en) | 1990-11-06 |
| JPS6414111A (en) | 1989-01-18 |
| EP0286034B1 (en) | 1991-03-20 |
| HUT46597A (en) | 1988-11-28 |
| EP0286034A1 (en) | 1988-10-12 |
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