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Dokumentenidentifikation EP0900179 07.08.2003
EP-Veröffentlichungsnummer 0900179
Titel VERWENDUNG VON POLYMEREN MIT HYDROXAMSÄUREGRUPPEN UM DIE BAYERSVERFAHRENKRUSTE ZU ÄNDERN
Anmelder Cytec Technology Corp., Wilmington, Del., US
Erfinder ROTHENBERG, S., Alan, Wilton, US;
AVOTINS, V., Peter, Easton, US;
COLE, Robert, Portland, US;
KULA, Frank, Danbury, US
Vertreter Diehl, Glaeser, Hiltl & Partner, 80333 München
DE-Aktenzeichen 69723257
Vertragsstaaten DE, ES, FR, GB, GR, IE, IT
Sprache des Dokument EN
EP-Anmeldetag 23.04.1997
EP-Aktenzeichen 979224359
WO-Anmeldetag 23.04.1997
PCT-Aktenzeichen PCT/US97/06886
WO-Veröffentlichungsnummer 0097041075
WO-Veröffentlichungsdatum 06.11.1997
EP-Offenlegungsdatum 10.03.1999
EP date of grant 02.07.2003
Veröffentlichungstag im Patentblatt 07.08.2003
IPC-Hauptklasse C02F 5/12
IPC-Nebenklasse C01F 7/47   B01D 21/01   C01F 7/06   

Beschreibung[en]
Background of the Invention

The Bayer Process for the purification of bauxite in the production of aluminum is well recognized. It is the most widely used process in the world and its process details are a matter of public knowledge.

During the processing of the bauxite in the Bayer Process, certain insoluble species are produced which have a tendency to deposit as scale on the walls of apparatus and equipment used in the process, such as pipes, digesters, pumps, heat exchangers, settlers, filters, etc. These species include titanates, silicates, trihydrates and the like. The silicates in the form of insoluble sodium aluminosilicates are often called DSP, desilication products. These species differ from plant-to-plant and from ore-to-ore and, in addition to existing as scale, exist in contaminant quantities in various streams of the process. The presence of these species is detrimental to the operation of the Bayer Process in that they constitute process losses. Additionally, scale deposition on equipment, apparatus, such as on the walls of the tubes of heat exchangers, digesters, settlers, filters and pipes substantially reduce their efficiency in that the flow of process streams through pipes is seriously impeded and the transfer of heat to the process stream is decreased. Currently, the removal of scale is accomplished by manual means such as jackhammers, dynamite, etc., which is very cost intensive.

Efforts have been initiated by commercial plants to find solutions to the problem of scale such as dilution, precipitation, etc., and by modifying the conditions under which certain stages of the Bayer Process are conducted.

For example, EPO Application No. 0582399A2 teaches the use of ammonium compounds, aromatic amine compounds and other amine compounds, all of specific formula, to alter silicious materials in the Bayer Process. Exemplary additives are tetramethylammonium hydroxide; amino tri(methylene) phosphoric acid; tripropylamine and the like. Similarly, in EPO Application No. 0586070 A2, polymeric quaternary ammonium compounds and polyamine compounds such as poly DADMACs and polyacrylamides are employed to alter siliceous materials in the Bayer Process liquors.

SUMMARY OF THE INVENTION

The instant invention relates to the use of hydroxamic acid or salt group containing polymers having a weight average molecular weight of from about 1,000 to less than about 10,000 to treat Bayer Process liquors containing a scale forming component so as to alter the morphology of said component and/or the scale formed thereby, thereby reducing the amount of scale formation and/or enhancing the removal of existing scale in Bayer Process apparatus and equipment.

The use of hydroxamic group containing polymers to eliminate the scaling by deposit of alkaline earth compounds such as those containing calcium, barium, etc., from an aqueous medium is taught in U.S. Patent No. 4,532,046. The patentees, however, do not indicate that these polymers are useful in the treatment of Bayer Process streams which involve titanates, silicates, etc., and which are at high temperature and pH, e.g. over 14.

Hydroxamic acid polymers are also known to be useful as corrosion inhibitors for use in, for example, industrial cooling waters which contain hardness, see U.S. Patent No. 5,308,498; however, the inhibition of corrosion in iron and steel alloys is attributable again to the presence of alkaline earth compounds, i.e., those containing calcium, magnesium, etc.

Additionally, high molecular weight polymers containing hydroxamic acid or salt groups are known to be effective flocculants in the Bayer Process for the removal of suspended solids. The polymers used for this purpose are, however, most often added to those streams of the Bayer Process which do not result in the debilitating scaling of equipment, apparatus, pipes, etc., see U.S. Patent No. 4,767,540 and Light Metals, 1991, Pages 167-171. As a result, this patentee does not indicate that the polymers disclosed therein are effective for scale alternation or deposition inhibition.

According to one aspect of the invention there is provided the use of a hydroxamic acid or salt group-containing polymer having a weight average molecular weight in the range from 1,000 to less than 10,000 and a degree of hydroxamation of from 10 to 90 percent for reducing the formation of scale in a Bayer Process liquor stream containing at least one scale-forming component selected from titanates, silicates and trihydrates, by adding to said liquor stream said polymer in an amount effective to inhibit said scale-forming component from depositing on said Bayer Process equipment, which is at least 0.1mg of polymer per litre of said liquor.

According to a second aspect of the invention there is provided the use of a hydroxamic acid or salt group-containing polymer having a weight average molecular weight in the range from 1,000 to less than 10,000 and a degree of hydroxamation of from 10 to 90 percent for enhancing the removal of scale, which comprises at least one insoluble species selected from titanates, silicates and trihydrates, from Bayer Process equipment, by adding said polymer to a liquor stream within an item of Bayer Process equipment in an amount effective to alter the morphology of said scale; which is at least 0.1mg of polymer per litre of said liquor.

The hydroxamic acid or salt group containing polymer can vary broadly in type and should be sufficiently stable to be effective under the high temperatures, e.g. 185 to 225°F and strong caustic conditions, e.g. 80 to 400 g./l. total alkali content expressed as sodium carbonate equivalent.

Any water-soluble hydroxamic acid or salt group containing polymer may be used, especially those containing pendant groups of the formula:

where R is hydrogen or a cation. The polymers can be derived from pendant ester, amide, anhydride, nitrile, etc., group containing polymers by the reaction thereof with a hydroxylamine or salt thereof.

Exemplary of polymers which may be reacted to impart the pendant hydroxamic acid or salt group thereon include acrylic, methacrylic, crotonic, etc., acid ester polymers such as those made from methyl acrylate, ethyl acrylate, t-butylacrylate, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, dimethyl aminoethylacrylate, methyl crotonate, etc; polymers of maleic anhydride and its esters; nitrile polymers such as those produced from acrylonitrile, methacrylonitrile, etc; amide polymers such as those produced from acrylamide, methacrylamide, etc., or copolymers terpolymers of the above esters, nitriles and amides, etc.

The hydroxamic acid or salt group containing polymers are well known in the art as exemplified by U.S. Patent Nos. 3,345,344; 4,480,067; 4,532,046; 4,536,296; and 4,587,306. The general procedure for their preparation comprises reacting the polymer containing the pendant reactive group, in solution, with a hydroxylamine or its salt at a temperature ranging from about 50°C to about 100°C for several hours at elevated pH. From 1 to 90% of the available pendant reactive groups of the polymer may be replaced by the hydroxamic acid or salt groups in this manner. The polymer to be hydroxamated may, in addition to being used in the form of an aqueous solution, be used in the form of a latex or an inverse emulsion. For example, an aqueous solution of acrylamide or an acrylamide and a comonomer e.g. acrylic acid can be added to a hydrocarbon oil in the presence of an appropriate emulsifier to provide a water-in-oil emulsion wherein the oil is the continuous phase and the monomer solution is the discontinuous phase. Polymerization of the polymer results in a water-in-oil emulsion wherein the oil is the continuous phase and the polymer solution is the discontinuous phase. Subsequent hydroxamation of the polymer results in a water-in-oil emulsion of the hydroxamated polymer which may be used as such in the present invention or inverted into water to form a dilute aqueous solution of hydroxamated polymer useful herein.

The polymers usetul herein should contain a degree of hydroxamation ranging from 10 to 90 mole percent, preferably from 10 to 75 mole percent, and most preferably from 10 to 50 mole percent.

Suitable hydroxylamine salts include the sulfates, sulfites, phosphates, perchlorates, hydrochlorides, acetates, propionates, etc., the reaction media being adjusted in pH to from about 3 to 14, preferably over 7.0 by means of acid or base addition to the solution.

Any water-soluble polymer may be used in the present process provided that it, after hydroxamation, performs to alter the morphology of the existing scale or scale forming component in the liquor thereby reducing the amount of scale formed and/or enhancing the removal of existing scale in the Bayer Process apparatus or equipment. Preferred polymers are copolymers of (alk) acrylamide with up to 95 mole percent of acrylic acid, sodium acrylate, methacrylic acid, methyfacrylate, etc.

The weight average molecular weight of the polymers useful in the present invention must range from about 1,000 to less than about 10,000, preferably from about 2,000 to about 9,000.

The hydroxamated polymer may be added directly to the apparatus, equipment, etc., in which the formation of scale is to be inhibited, modified, etc., such as the slurry mixers, digesters, flash tanks, settlers, filters, sand trap cyclones, etc. It is preferred, however, that the hydroxamated polymer be added to a charge stream or recycle stream or liquor leading to any of this apparatus or equipment.

The amount of hydroxamated polymer added depends primarily on the content of the liquor involved and generally all that is required is a scale inhibiting amount thereof. Generally, however, at least 0.1 mg. of the hydroxamated polymer per liter of the liquor should be used, preferably at least 1.0 mg./liter.

Higher or lower amounts of hydroxamated polymer than set forth above may be used and still fall within the scope of the present invention.

The following examples are set forth for purposes of illustration only and are not to be construed as limitations on the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.

Example 1 Titanate Scale

A series of laboratory digestions is carried out with varying levels of hydroxamated polymers added to a prepared slurry. For each digestion, 125 grams of a simulated digester medium and varying amounts of a hydroxamated polymer are prepared. The hydroxated polymer has a weight average molecular weight of about 1,500 and contains about 70% hydroxamate functional groups. The simulated medium is heated to 143°C for 15 minutes. After cooling to about 90°C, the resulting slurries are filtered. The filtrates are placed in storage vessels and monitored for precipitation of scale on the walls of the storage container. The results are set forth immediately below. Example Polymer Dosage Scale 1A 0 Scaling on interior surfaces 1B 20 ppm Minor scaling 1C 100 ppm Very minor scaling

Example 2 Titanate Scale Reduction

To a strong liquor recovered from the concentration of spent liquor from the Bayer Process is added 100 ppm of hydroxamated (58%) polyacrylamide having a molecular weight of about 8,000. No scale is detected after extended storage, however a sample containing no hydroxamated polymer exhibits noticeable scaling.


Anspruch[de]
  1. Verwendung eines Polymers, das Hydroxamsäure oder - salzgruppen enthält und ein gewichtsmittleres Molekulargewicht im Bereich von 1.000 bis unter 10.000 und einen Hydroxamierungsgrad von 10 bis 90 Prozent aufweist, zur Verringerung der Bildung von Ablagerungen in einem Flüssigkeitsstrom des Bayer-Verfahrens, in dem mindestens ein Ablagerungen bildender Bestandteil enthalten ist, der aus Titanat, Silikat oder Trihydrat gewählt ist, indem diesem Flüssigkeitsstrom das Polymer in einer Menge, die wirksam ist, um diesen Ablagerungen bildenden Bestandteil am Ablagern an der Apparatur dieses Bayer-Verfahrens, die mindestens 0,1 mg Polymer pro Liter dieser Flüssigkeit beträgt, zu inhibieren.
  2. Verwendung eines Polymers, das Hydroxamsäure oder - salzgruppen enthält und ein gewichtsmitttleres Molekulargewicht im Bereich von 1.000 bis unter 10.000 und hat einen Hydroxamierungsgrad von 10 bis 90 Prozent hat, zur Verstärkung der Entfernung von Ablagerungen, die mindestens eine unlösliche Spezies aufweisen, die aus Titanat, Silikat und Trihydrat gewählt ist, von Apparaturen des Bayer-Verfahrens, indem dieses Polymer zu einem Flüssigkeitsstrom innerhalb eines Elements des Apparats des Bayer-Verfahrens in einer Menge zugegeben wird, die wirksam ist, um die Morphologie dieser Ablagerungen zu verändern, die mindestens 0,1 mg Polymer pro Liter Flüssigkeit beträgt.
  3. Verwendung gemäß Anspruch 1 oder Anspruch 2, wobei diese Ablagerung oder der die Ablagerungen bildende Bestandteil ein Natrium-Aluminiumsilikat ist.
  4. Verwendung gemäß einem der vorstehenden Ansprüche, wobei der Flüssigkeitsstrom ein verbrauchter Flüssigkeitsstrom ist.
  5. Verwendung gemäß einem der Ansprüche 1 bis 3, wobei dieses Element des Apparats des Bayer-Verfahrens ein Schlammmischer oder ein hierzuführender Beschickungsgutstrom oder zirkulierender Strom ist.
  6. Verwendung gemäß einem der Ansprüche 1 bis 3, wobei dieses Element des Apparats des Bayer-Verfahrens ein Flash-Tank ist, ein hierzuführender Beschickungsgutstrom oder ein zirkulierender Strom ist.
  7. Verwendung gemäß einem der Ansprüche 1 bis 3, wobei dieses Element des Apparats des Bayer-Verfahrens ein Autoklav ist, ein hierzuführender Beschickungsgutstrom oder ein zirkulierender Strom ist.
  8. Verwendung gemäß einem der Ansprüche 1 bis 3, wobei dieses Element des Apparats des Bayer-Verfahrens ein Sandabscheidezyklon ist, ein hierzuführender Beschickungsgutstrom oder ein zirkulierender Strom ist.
  9. Verwendung gemäß einem der Ansprüche 1 bis 3, wobei dieses Element des Apparats des Bayer-Verfahrens ein Wärmeaustauscher ist, ein hierzuführender Beschickungsgutstrom oder ein zirkulierender Strom ist.
  10. Verwendung gemäß einem der vorhergehenden Ansprüche, wobei dieses Polymer einen Hydroxamierungsgrad im Bereich von 10 bis 50 Molprozent aufweist.
  11. Verwendung gemäß einem der vorhergehenden Ansprüche, wobei dieses Polymer in einer Menge von mindestens 1,0 mg pro Liter dieser Flüssigkeit zugefügt wird.
Anspruch[en]
  1. The use of a hydroxamic acid or salt group-containing polymer having a weight average molecular weight in the range from 1,000 to less than 10,000 and a degree of hydroxamation of from 10 to 90 percent for reducing the formation of scale in a Bayer Process liquor stream containing at least one scale-forming component selected from titanates, silicates and trihydrates, by adding to said liquor stream said polymer in an amount effective to inhibit said scale-forming component from depositing on said Bayer Process equipment, which is at least 0.1mg of polymer per litre of said liquor.
  2. The use of a hydroxamic acid or salt group-containing polymer having a weight average molecular weight in the range from 1,000 to less than 10,000 and a degree of hydroxamation of from 10 to 90 percent for enhancing the removal of scale, which comprises at least one insoluble species selected from titanates, silicates and trihydrates, from Bayer Process equipment, by adding said polymer to a liquor stream within an item of Bayer Process equipment in an amount effective to alter the morphology of said scale; which is at least 0.1mg of polymer per litre of said liquor.
  3. The use as claimed in Claim 1 or Claim 2 in which said scale or scale forming component is a sodium aluminosilicate.
  4. The use as claimed in any preceding Claim in which said liquor stream is a spent liquor stream.
  5. The use as claimed in any one of Claims 1 to 3 in which said item of Bayer Process equipment is a slurry mixer or a charge or recycle stream leading thereto.
  6. The use as claimed in any one of Claims 1 to 3 in which said item of Bayer Process equipment is a flash tank, or a charge or recycle stream leading thereto.
  7. The use as claimed in any one of Claims 1 to 3 in which said item of Bayer Process equipment is a digester, or a charge or recycle stream leading thereto.
  8. The use as claimed in any one of Claims 1 to 3 in which said item of Bayer Process equipment is a sand trap cyclone, or a charge or recycle stream leading thereto.
  9. The use as claimed in any one of Claims 1 to 3 in which said item of Bayer Process equipment is a heat exchanger, or a charge or recycle stream leading thereto.
  10. The use as claimed in any preceding Claim in which said polymer has a degree of hydroxamation in the range of 10 to 50 mole percent.
  11. The use as claimed in any preceding Claim in which said polymer is added in an amount of at least 1.0mg per litre of said liquor.
Anspruch[fr]
  1. Utilisation d'un polymère contenant un groupement acide hydroxamique ou un de ses sels possédant un poids moléculaire moyen en poids dans la gamme comprise entre 1000 et moins de 10000 et un degré d'hydroxamation compris entre 10 et 90 pourcent pour réduire la formation de dépôt dans un courant d'effluent de Procédé Bayer contenant au moins un composant formant un dépôt choisi parmi titanates, silicates et trihydrates, par addition audit courant d'effluent dudit polymère en une quantité efficace pour inhiber le dépôt dudit composant formant un dépôt sur ledit équipement du Procédé Bayer, d'au moins 0,1 mg de polymère par litre dudit effluent.
  2. Utilisation d'un polymère contenant un groupement acide hydroxamique ou un de ses sels possédant un poids moléculaire moyen en poids dans la gamme comprise entre 1000 et moins de 10000 et un degré d'hydroxamation compris entre 10 et 90 pourcent pour augmenter l'élimination de dépôt de l'équipement du Procédé Bayer, ce dit dépôt comprenant au moins une espèce insoluble choisie parmi titanates, silicates et trihydrates, par addition dudit polymère au courant d'effluent à l'intérieur d'un élément de l'équipement du Procédé Bayer en une quantité efficace pour modifier la morphologie dudit dépôt d'au moins 0,1 mg de polymère par litre dudit effluent.
  3. Utilisation selon la revendication 1 ou la revendication 2 dans laquelle ledit dépôt ou ledit composant formant un dépôt est un aluminosilicate de sodium.
  4. Utilisation selon l'une quelconque des revendications précédentes dans laquelle ledit courant d'effluent est un courant d'effluent usé.
  5. Utilisation selon l'une quelconque des revendications 1 à 3 dans laquelle ledit élément d'équipement de Procédé Bayer est un mélangeur de suspension épaisse ou une charge ou un courant de recyclage conduisant à celui-ci.
  6. Utilisation selon l'une quelconque des revendications 1 à 3 dans laquelle ledit élément d'équipement de Procédé Bayer est une citerne ou une charge ou un courant de recyclage conduisant à celle-ci.
  7. Utilisation selon l'une quelconque des revendications 1 à 3 dans laquelle ledit élément d'équipement de Procédé Bayer est un digesteur ou une charge ou un courant de recyclage conduisant à celui-ci.
  8. Utilisation selon l'une quelconque des revendications 1 à 3 dans laquelle ledit élément d'équipement de Procédé Bayer est un cyclone désensableur ou une charge ou un courant de recyclage conduisant à celui-ci.
  9. Utilisation selon l'une quelconque des revendications 1 à 3 dans laquelle ledit élément d'équipement de Procédé Bayer est un échangeur de chaleur ou une charge ou un courant de recyclage conduisant à celui-ci.
  10. Utilisation selon l'une quelconque des revendications précédentes dans laquelle ledit polymère possède un degré d'hydroxamation compris dans la gamme de 10 à 50 mole pourcent.
  11. Utilisation selon l'une quelconque des revendications précédentes dans laquelle ledit polymère est ajouté en une quantité d'au moins 1,0 mg par litre dudit effluent.






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