Surfactant based small molecules for reducing aluminosilicate scale in the bayer process
Abstract
A method of reducing the scale containing aluminosilicate in a Bayer process comprising: adding to a Bayer liquor a scale reducing amount of the aluminosilicate scale of a non-polymeric reaction product resulting from the reaction of: a surfactant, a binder of amine, an epoxide binder and a glycidoxyalkyltrimethoxysilane, where the surfactant is dodecyl-1,3-propanediamine,

Term
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Projected expiry 31 December 2034, counted from filing; an application has no term until it is granted.
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7 claims: 1 independent, 6 dependent
- 1ES 2 835 705 T3 REIVINDICACIONES 1. Un método para reducir la incrustación que contiene aluminosilicato en un proceso de Bayer que comprende:añadir a un licor de Bayer una cantidad reductora de la incrustación del aluminosilicato de un producto de la reacción no polimérico resultante de la reacción de: un tensioactivo, un aglutinante de amina, un aglutinante de epóxido y un glicidoxialquiltrimetoxisilano, en donde el tensioactivo es la dodecil-1,3-propanodiamina,
- 2El método de acuerdo con la reivindicación 1, en donde el glicidoxialquiltrimetoxisilano es el 3- glicidoxialquiltrimetoxisilano.
- 3El método de acuerdo con la reivindicación 1, en donde el aglutinante de epóxido es una molécula de acuerdo con las Fórmulas (I), (II) y cualquier combinación de estas:
- 4El método de acuerdo con la reivindicación 1, en donde el producto de la reacción no polimérico resulta de la reacción del tensioactivo que es la dodecil-1,3-propanodiamina, el aglutinante de amina, el aglutinante de epóxido, el glicidoxialquiltrimetoxisilano y un hidrófobo que es un glicidil éter alifático C8-C10.
- 5El método de acuerdo con la reivindicación 1, en donde el producto de la reacción tiene un peso molecular de menos de 500 g/mol (daltons).
- 6El método de acuerdo con la reivindicación 1, en donde el producto de la reacción es
- 7El método de acuerdo con la reivindicación 1, en donde el aglutinante de amina es uno que se selecciona de la lista que consiste en:tetraetilenpentamina y etilendiamina.
Independent claims7
269 paragraphs in 15 sections, as filed
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DESCRIPTION
Small molecules based on surfactants to reduce the scaling of the aluminosilicate in the Bayer process
Background of the invention
The invention relates to methods for improving the treatment and inhibition of scale in various streams of industrial processes, in particular to certain small molecules based on surfactants that have been found to be particularly effective in treating the scale of aluminosilicate. in a Bayer process stream.
As described inter alia in US Patent No. 6,814,873, the Bayer process is used to make alumina from bauxite ore. The process uses a caustic solution to extract the soluble alumina values from the bauxite. After dissolution of the alumina values from the bauxite and removal of the insoluble waste material from the process stream, the soluble alumina precipitates as solid alumina trihydrate. The remaining caustic solution known as liquor and / or waste liquor is recycled to the previous stages of the process and used to treat the fresh bauxite. This thus forms a fluid circuit. For the purposes of this application, this description defines the term liquor. However, recycling the liquor within the fluid circuit has its own complexities.
Bauxite often contains silica in various forms and amounts. Some of the silica is not reactive, so it does not dissolve and remains a solid material within the Bayer circuit. Other forms of silica (eg clays) are reactive and dissolve in caustic when added to liquors from the Bayer process, thereby increasing the concentration of silica in the liquor. As the liquor repeatedly flows through the Bayer process loop, the concentration of silica in the liquor increases further, to a point where it reacts with the aluminum and soda to form insoluble aluminosilicate particles. Solid aluminosilicate is observed in at least two forms, sodalite and cancrinite. These and other forms of aluminosilicate are commonly referred to, and for the purposes of this application define, the terms "desilication product" or "DSP".
The DSP can have a formula of 3 (Na2O ^ Al2O '^ 2SO2 ^ 0-2 H2O) · 2NaX where X represents OH<sup>-</sup>, Cl<sup>-</sup>, CO3<sup>2</sup>, SO4<sup>2-</sup>. Because DSP has inverse solubility (precipitation increases at higher temperatures) and can precipitate as fine scale of hard insoluble crystalline solids, its accumulation in Bayer process equipment is problematic. As DSP accumulates in pipes, vessels, heat transfer equipment, and other Bayer process equipment, it forms bottlenecks and flow obstructions and can adversely affect liquor performance. In addition, due to its thermal conductivity properties, DSP scale on heat exchanger surfaces reduces the efficiency of heat exchangers.
These adverse effects are typically managed through a decalcification regimen, which involves the process equipment being shut down and scale is treated and physically or chemically removed. One consequence of this type of system is significant and regular downtime for critical equipment. Furthermore, as part of the descaling process, the use of dangerous concentrated acids such as sulfuric acid is often employed and this constitutes an undesirable safety hazard.
Another way Bayer's process operators manage the build-up of silica concentration in the liquor is to deliberately precipitate the DSP as free crystals rather than scale. Typically, a desilication step is used in the Bayer process to reduce the concentration of silica in solution by precipitating silica as the DSP, as a free precipitate. While such desilication reduces the overall concentration of silica within the liquor, the complete removal of all silica from the solution is impractical and the changing process conditions within various parts of the circuit (for example, within heat exchangers) can lead to changes in the solubility of the DSP, resulting in consequent precipitation as scaling.
Previous attempts to control and / or reduce scaling of DSP in the Bayer process have included the addition of polymeric materials containing three alkyloxy groups attached to a silicon atom as described in US Pat. 6,814,873 B2, US Published Application Nos. 2004/0162406 A1, 2004/0011744 A1, 2005/0010008 A2, published international application no. WO 2008/045677 A1, and the published article Max HTTM Sodalite Scale Inhibitor: Plant Experience and Impact on the Process, by Donald Spitzer et al., Pages 57-62, Light Metals 2008, (2008).
However, the manufacture and use of these trialkoxysilane grafted polymers can involve undesired degrees of viscosity, making it difficult to handle and disperse the polymer through the Bayer process liquor. Other previous attempts to address scale build-up are described in US Patent Nos. 5,650,072 and 5,314,626.
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United States published application no. 2012/148462 A1 provides a method to inhibit the build-up of DSP scale in the liquor circuit of Bayer process equipment. The method includes the addition of one or more particular silane-based small molecules to the fluid circuit of the liquor. These scale inhibitors reduce DSP scale formation and therefore increase fluid performance, increase the amount of time Bayer process equipment can be operational, and reduce the need for costly acid washes and hazardous equipment from Bayer process equipment. As a result, the method provides a significant reduction in the total cost of operation of a Bayer process.
Therefore, while a variety of methods are available to Bayer process operators to manage and control the formation of DSP scale, there is a clear need and utility for an improved method to prevent or reduce scale formation of the DSP. DSP in Bayer process equipment.
Brief summary of the invention
To meet the long-term unmet needs identified above, at least one embodiment of the invention is directed toward a method of reducing aluminosilicate scaling in a Bayer process comprising the step of adding a reducing amount of the fouling of the aluminosilicate of a non-polymeric reaction product resulting from the reaction of: a surfactant, an amine binder, an epoxy binder, and a glycidoxyalkyltrimethoxysilane (GPS), wherein the surfactant is 1,3-dodecyl-propanediamine.
The non-polymeric reaction product can be a result of the reaction of the above elements that further comprise at least one hydrophobic. The GPS can be 3-glycidoxypropyltrimethoxysilane. The epoxy binder can be a molecule according to Formulas (I), (II) and any combination of these:
<img file="ES2835705T3_D0001.tif" />
The hydrophobe can be a C8-C10 aliphatic glycidyl ether. The reaction product can have a molecular weight of less than 500 g / mol (daltons). The reaction product can be in accordance with the formula illustrated in Figure 2.
The reaction product can be formed at least in part according to one of the methods selected from the group consisting of Methods: IV, V, VI, VII, VIII, IX, X, XI, XII and XIII, and any combination of these. The amine binder can be one selected from the list consisting of: tetraethylenepentamine and ethylenediamine.
Additional features and advantages are described in the present description and will be apparent from the following detailed description.
Brief description of the drawings
A detailed description of the invention is described below with specific reference to the drawings in which:
FIGURE 1 is an illustration of the formula of reaction product X (not in accordance with the invention as currently claimed).
FIGURE 2 is an illustration of the formula for reaction product BB.
FIGURE 3 is a first table of types of formulas used in the invention (not according to the invention as currently claimed).
FIGURE 4 is a second table of types of formulas used in the invention.
FIGURE 5 is a third table of types of formulas used in the invention.
FIGURE 6 is a fourth table of types of formulas used in the invention
FIGURE 7 is an illustration of SEM (scanning electron microscope) analysis demonstrating the efficacy of the invention.
Detailed description of the invention
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The following definitions are provided to determine how the terms used in this application should be interpreted and, in particular, how the claims should be interpreted.
Polymer means a chemical compound that essentially comprises repeating structural units each containing two or more atoms. While many polymers have large molecular weights of more than 500, some polymers, such as polyethylene, can have molecular weights of less than 500. Polymer includes copolymers and homopolymers.
Small molecule means a chemical compound that essentially comprises non-repeating structural units. Because an oligomer (with more than 10 repeating units) and a polymer are essentially made up of repeating structural units, they are not small molecules. Small molecules can have molecular weights greater than or less than 500. The terms small molecule and polymer are mutually exclusive.
Fouling means a deposit of material that accumulates on equipment during the operation of a chemical and / or manufacturing process that may be unwanted and that may affect the cost and / or efficiency of the process. DSP is a type of inlay.
Amine means a molecule that contains one or more nitrogen atoms and that has at least one secondary amine or primary amine group. By this definition, monoamines like dodecylamine, diamines like hexanediamine, and triamines like diethylenetriamine are all amines.
GPS is glycidoxyalkyltrimethoxysilane which includes 3-glycidoxypropyltrimethoxysilane, a possible formula for GPS can be represented by the structure:
O ^ Yes (OR)<sub>3</sub>
Ethoxylated alcohol means an alcohol according to the formula:
R- (EO) n-OH where EO is an ethoxy group (-OCH2CH2-) and n is an integer within the range 1-50.
Ethoxylated amine means an amine according to the formula:
^ (EOk-OH
R— (EO), - OH where EO is an ethoxy group (-OCH2CH2-), m is an integer within the range 1-50, and n is an integer within the range 1-50.
G12A7 means a C12-C14 nonionic alcohol ethoxylate surfactant, a representative example of which is
Teric G12A7, sold by Huntsman.
G12A4 means a C12-C14 nonionic alcohol ethoxylate surfactant, a representative example of which is
Teric G12A4, sold by Huntsman.
G17A3 means a C16-C18 straight chain nonionic alcohol ethoxylate surfactant, a representative example of which is Teric G17A3, sold by Huntsman.
G9A6 means a C9-C11 straight chain nonionic alcohol ethoxylate surfactant, a representative example of which is Teric G9A6, sold by Huntsman.
G9A8 means a C9-C11 straight chain nonionic alcohol ethoxylate surfactant, a representative example of which is Teric G9A8, sold by Huntsman.
18M20 means a C18-C22 alkyl amine ethoxylate surfactant, a representative example of which is Teric
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18M20, sold by Huntsman.
18M2 means a C18-C22 alkyl amine ethoxylate surfactant, a representative example of which is Teric 18M2, sold by Huntsman.
16M2 means a C16-C18 alkyl amine ethoxylate surfactant, a representative example of which is Teric 16M2, sold by Huntsman.
TAM5 means a tallow alkyl amine ethoxylate surfactant, a representative example of which is Agnique TAM5, sold by Cognis.
DPD stands for dodecyl-1,3-propanediamine
EGDGE stands for ethylene glycol diglycidyl ether
OPD stands for oleyl-1,3-propanediamine
EPI stands for epichlorohydrin
OA stands for octylamine
ED stands for ethylenediamine
OLA stands for oleylamine
TEPA stands for tetraethylenepentamine
AGE means C8-C10 aliphatic glycidyl ether
Alkyloxy means it has the structure of OX where X is a hydrocarbon and O is oxygen. It can also be used interchangeably with the term alkoxy. Typically, in this application, oxygen is attached to both the X group and a silicon atom of the small molecule. When X is Ci, the alkyloxy group consists of a methyl group attached to the oxygen atom. When X is C2, the alkyloxy group consists of an ethyl group attached to the oxygen atom. When X is C3, the alkyloxy group consists of a propyl group attached to the oxygen atom. When X is C4, the alkyloxy group consists of a butyl group attached to the oxygen atom. When X is C5, the alkyloxy group consists of a pentyl group attached to the oxygen atom. When X is C6, the alkyloxy group consists of a hexyl group attached to the oxygen atom.
Monoalkyloxy means that attached to a silicon atom is an alkyloxy group.
Dialkyloxy means that attached to a silicon atom are two alkyloxy groups.
Trialkyloxy means that attached to a silicon atom are three alkyloxy groups.
Synthetic liquor or synthetic waste liquor is a liquid generated in the laboratory that is used for experimentation, whose composition with respect to alumina, soda and caustic corresponds to the liquor produced by recycling through the Bayer process.
Bayer liquor is a real liquor that has undergone a Bayer process in an industrial facility.
Separation means a mass transfer process that converts a mixture of substances into two or more different product mixtures, at least one of which is enriched in one or more of the constituents of the mixture, this includes, but is not limited to , processes such as: adsorption, centrifugation, cyclonic separation, density-based separation, chromatography, crystallization, decantation, distillation, drying, electrophoresis, elutriation, evaporation, extraction, leach extraction, liquid-liquid extraction, solid phase extraction, flotation, air flotation dissolved, foam flotation, flocculation, filtration, mesh filtration, membrane filtration, microfiltration, ultrafiltration, nanofiltration, reverse osmosis, fractional distillation, fractional freezing, magnetic separation, precipitation, recrystallization, sedimentation, gravity separation, sieving, pickling, sublimation, vapor-liquid separation, winnowing, refining zone and any combination of these.
Thickener or settler means a container used to effect a solid-liquid separation of a suspension, often with the addition of flocculants, the container constructed and arranged to receive a suspension retains the suspension for a period of time sufficient to allow the solid parts of the suspension settle downwards (underflow) away from a more liquid part of the suspension (overflow), decant the overflow and eliminate the underflow. The underflow and overflow of the
ES 2 835 705 T3 thickeners are often passed to filters to further separate solids from liquids.
In Bayer's process for making alumina, the bauxite ore goes through a milling stage and the alumina, along with some impurities, including silica, are dissolved in the added liquor. The mixture then typically goes through a desilification stage where the silica is deliberately precipitated as the DSP to reduce the amount of silica in the solution. The suspension is passed to a digestion stage where any remaining reactive silica dissolves, thereby again increasing the concentration of silica in the solution, which can subsequently form more DSP as the process temperature increases. Subsequently, the liquor is separated from the undissolved solids and the alumina is recovered by precipitation as gibbsite. The waste liquor completes its circuit when it passes through a heat exchanger and returns to the grinding stage. DSP scale builds up throughout the Bayer process but particularly in the digestion stage and more particularly in or near the heat exchanger, where the recycled liquor passes.
In this invention, it was discovered that dosing of various types of small molecule based products can reduce the amount of DSP scale formed. Small molecules are products of the reaction of surfactants with GPS, amine binders, and epoxy binders. Figure 2 shows a representative structure of a small molecule made up of combinations of surfactant, GPS, epoxy binder, and amine binder and is an example of the possible combination of reaction products encompassed by this embodiment. In at least one embodiment of the invention, an effective concentration of the small molecule product is added at some point or stage in the liquor circuit of the Bayer process, which minimizes or avoids the accumulation of DSP in the vessels or equipment thereon. along the liquor circuit.
As described in US Patent No. 8,545,776, the small molecule DG12 is an example of a small molecule that is a product of the reaction of a surfactant and GPS. Similarly, the small molecule TG14 also in US Patent No. 8,545,776, and the various small molecules, such as GEN1, GEN2, and GEN3, which are described in US published patent application nos. 2011/0212006 and 2012/0148462 are products of the reaction of some of these elements. The invention excludes TG14, DG12, GEN1, GEN2 and GEN3.
<img file="ES2835705T3_D0002.tif" />
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<img file="ES2835705T3_D0003.tif" />
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In at least one embodiment, the reaction product is formed at least in part by allowing two or more of the reagents to come into contact with each other for a period of time between 1 minute and 55 days, and / or by allowing the reagents to enter. in contact with each other at a temperature between 20 ° C and 500 ° C. The invention encompasses the addition of any of some or all of the reagents to the reaction simultaneously and / or in any sequential order. Any part of the reaction can occur within one or more of: a liquid medium, a water medium, in the presence of acid and / or base, and / or under acidic, basic or neutral conditions. Any part of the reaction can occur at least in part in the presence of one or more catalysts.
Figure 4, Figure 5, and Figure 6 are tables illustrating some of the possible combinations of reaction products encompassed by this embodiment.
In at least one embodiment, the epoxy binder is in accordance with one or more of Formulas (I) and (II):
<img file="ES2835705T3_D0004.tif" />
In at least one embodiment, the hydrophobe is a C8-C10 aliphatic glycidyl ether. The hydrophobic can be described as a straight or branched aromatic or aliphatic hydrocarbon chain, which may optionally contain an additional functional end group or ether bond, such as an epoxide that allows the hydrophobe to react and bind to other molecules. The hydrocarbon chain can consist of between 3 and 50 carbon atoms.
In at least one embodiment, the hydrophobe agrees with Formula (III) where R 'is a straight or branched hydrocarbon chain containing at least 3 carbon atoms:
<img file="ES2835705T3_D0005.tif" />
In at least one embodiment, the amine binder is selected from linear or branched, aliphatic or cycloaliphatic monoamines, diamines, triamines, butamines and pentamines. It is preferred that the total number of carbon atoms in the amine be less than 30 and more preferred that it be less than 20. In at least one embodiment, the amine is selected from a list consisting of: tetraethylenepentamine, ethylenediamine, and any combination of these.
In at least one embodiment, a small amine molecule is reacted with both 3-glycidoxypropyltrialkoxysilane (GPS) and a hydrophobic molecule to form a DSP inhibiting composition. The hydrophobic molecule is an amine-reactive compound that has an amine-reactive functional group, such as glycidyl, chlorine, bromine, or isocyanate groups. In addition to the amine-reactive group, the hydrophobic molecule has at least one straight or branched C3-C22 hydrophobic carbon chain, aromatic or aliphatic.
In at least one embodiment, the amine molecule is selected from linear or branched, aliphatic or cycloaliphatic monoamines or diamines. It is preferred that the total number of carbon atoms in the amine is less than 30 and more preferred that it is less than 20.
In at least one embodiment, the amine is selected from a list consisting of: isophorondiamine, xylenediamine, bis (aminomethyl) cyclohexane, hexanediamine, C, C, C-trimethylhexanediamine, methylene bis (aminocyclohexane), saturated fatty amines, unsaturated fatty amines, such as oleylamine and soybean, fatty N-1,3-propanediamine, such such as cocoalkyl propanediamine, oleyl propanediamine, dodecyl propanediamine, hydrogenated tallowalkyl propanediamine and tallowalkyl propanediamine and any combination thereof.
Not according to the invention as currently claimed, the reaction product is Product P, which is a product of the reaction of GPS with a surfactant having a formula of:
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<img file="ES2835705T3_D0006.tif" />
Not according to the invention as currently claimed, the reaction product is Product U, which is a product of the reaction of GPS with a surfactant and a hydrophobe having a formula of:
RO ^ /<sup>OR</sup>
<img file="ES2835705T3_D0007.tif" />
Not in accordance with the invention as currently claimed, the reaction product is Product X, which is a product of the reaction of GPS with a surfactant, a hydrophobic and an epoxy binder having a formula illustrated in Figure 1 .
In at least one embodiment, the reaction product is Product BB, which is a reaction product of GPS with a surfactant, a hydrophobic, an epoxy binder, and an amine binder having the formula illustrated in Figure 2. .
In at least one embodiment, the reaction conditions result in the formation of two or more of the aforementioned reaction products. In at least one embodiment, the composition introduced to address the DSP contains one, two, or more of the reaction products mentioned above.
In at least one embodiment, the resulting surfactant-based small molecules are added to a dilute caustic solution prior to addition to the process stream.
These small molecules reduce the amount of DSP scale formed and therefore prevent its build-up in Bayer process equipment.
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The efficacy of these small molecules was unexpected as the prior art teaches that only high molecular weight polymers are effective. The effectiveness of the polymer was assumed to depend on its hydrophobic nature and size. This was confirmed by the fact that cross-linked polymers are even more efficient than single-chain polymers. As a result, it was assumed that small molecules only serve as building blocks for these polymers and are not effective in their own right. (Document No. WO 2008/045677 [0030]). Furthermore, the scientific literature states that small molecules that contain ... a Si-O3 group are not effective in preventing scaling of sodalite ... because ... the bulky group ... is essential to prevent the molecule is incorporated into the growing sodalite. Page 57 9 Light Metals 2008, (2008). However, it has recently been discovered that in fact, as further explained in the provided examples, small molecules such as those described in the present disclosure are indeed effective in reducing DSP fouling.
It is believed that there are at least three advantages to using a small molecule based inhibitor as opposed to a polymeric inhibitor with multiple silane and hydrophobic repeating units. A first advantage is that the smaller molecular weight of the product means that there are a greater number of active inhibitory moieties available around the DSP seed crystal sites at the DSP formation stage. A second advantage is that the lower molecular weight allows a higher rate of diffusion of the inhibitor, which in turn favors the rapid binding of the inhibitor molecules to the DSP seed crystals. A third advantage is that the lower molecular weight prevents high product viscosity and thus makes handling and injection into the Bayer process stream more convenient and efficient.
In at least one embodiment, embedding of the DSP is addressed using one or more of the application methods described in US Patent Application Nos. 13 / 035,124, 13 / 403,282, 13 / 791,577, 14 / 011,051, US Patent Nos. 5,314,626, 6,814,873, 7,390,415, 7,442,755, 7,763,698, International Patent Application Nos. WO 02/070411, WO 2008/045677, WO 2012/115769, and US Published Patent Application Nos. 2004/0162406, 2004/0011744, 2010/0256317, 2011/0076209,
2011/0212006 and 2012/0148462.
Examples
Various reaction products were produced using the reagents listed in Figure 3, Figure 4, and Figure 5 according to the various methods described below. The mass of surfactant added to all reactions was 5 g. The masses of other reagents were calculated from the mole ratios described in Figures 3, 4 and 5. Hydroxy terminated surfactants (not in accordance with the invention as currently claimed)
Method I (not according to the invention as currently claimed): A mixture of the surfactant (dihydroxy terminated) and the hydrophobic was stirred and heated to 65 ° C. A NaOH solution (50% in water) was added and the mixture was left for 30 min at 65 ° C. Then the glycidoxypropyltrimethoxysilane was added and the mixture was left for 2 hours at 65 ° C. The reaction mixture was cooled and then diluted 5% w / w in a 20 g / l NaOH solution.
• NaOH was added at 2 molar equivalents to the added epoxide.
• For products A - O, Method I was used excluding the incorporation of hydrophobes.
Amino-terminated surfactants
Method II (not according to the invention as currently claimed): The surfactant was stirred and heated to 65 ° C. Hydrophobic was added and the mixture was left for 30 min at 65 ° C. Then the glycidoxypropyltrimethoxysilane was added and the mixture was left for 2 hours at 65 ° C. The reaction mixture was cooled and then diluted 5% w / w in a 20 g / l NaOH solution.
• For products P and Q, Method II was used excluding the incorporation of the hydrophobic.
Method III (not according to the invention as currently claimed): The surfactant was stirred and heated to 65 ° C. The epoxy binder was added and the mixture was left for 30 min at 65 ° C. Then the glycidoxypropyltrimethoxysilane was added and the mixture was left for 2 hours at 65 ° C. The reaction mixture was cooled and then diluted 5% w / w in a 20 g / l NaOH solution. Method IV: A mixture of surfactant and amine binder was stirred and heated to 65 ° C. The epoxy binder was added and the mixture was left for 30 min at 65 ° C. Then the glycidoxypropyltrimethoxysilane was added and the mixture was left for 2 hours at 65 ° C. The reaction mixture was cooled and then diluted 5% w / w in a 20 g / l NaOH solution.
• Products EE and FF were allowed to react for 60 min at 65 ° C before the addition of glycidoxypropyltrimethoxysilane.
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Method V: A mixture of surfactant and amine binder was stirred and heated to 65 ° C. The epoxy binder was slowly added to the mixture and then left for a total of 2 h at 65 ° C. Then the glycidoxypropyltrimethoxysilane was added slowly and the mixture was left for a total of 1 hour at 65 ° C. The reaction mixture was cooled and then diluted 5% w / w in a 20 g / l NaOH solution.
Method VI: A mixture of surfactant, amine binder and DMSO was stirred and heated to 65 ° C. The epoxy binder was slowly added to the mixture and then left for a total of 3 hours at 65 ° C. Next, the glycidoxypropyltrimethoxysilane was slowly added to the mixture. After 30 min, a sample of the reaction mixture was taken and slowly added to a stirred solution of NaOH 20 g / l, diluting the sample to a concentration of 13.3% w / w.
Method VII: A mixture of surfactant and amine binder was stirred and heated to 65 ° C. The epoxy binder was slowly added to the mixture and then left for a total of 30 minutes at 65 ° C. The glycidoxypropyltrimethoxysilane was then slowly added to the mixture. After 19 min, a sample of the reaction mixture was taken and slowly added to a stirred solution of NaOH 20 g / l, diluting the sample to a concentration of 10% w / w.
Method VIII: A mixture of surfactant and amine binder was stirred and heated to 65 ° C. The epoxy binder was slowly added to the mixture and then left for a total of 1 hour at 65 ° C. Next, the glycidoxypropyltrimethoxysilane was slowly added to the mixture. After 15 min, a sample of the reaction mixture was taken and slowly added to a stirred solution of NaOH 20 g / l, diluting the sample to a concentration of 10% w / w.
Method IX: A mixture of surfactant, amine binder and DMSO was stirred and heated to 65 ° C. The epoxy binder was slowly added to the mixture and then left for a total of 1 hour at 65 ° C. The glycidoxypropyltrimethoxysilane was then slowly added to the mixture and the mixture was left for 1 hr. The reaction mixture was cooled and then diluted 10% w / w in a 20 g / l NaOH solution.
Method X: A mixture of surfactant, amine binder and DMSO was stirred and heated to 65 ° C. The epoxy binder was slowly added to the mixture and then left for a total of 3 hours at 65 ° C. The glycidoxypropyltrimethoxysilane was then slowly added to the mixture. After 16 min, a sample of the reaction mixture was taken and slowly added to a stirred solution of NaOH 20 g / L, diluting the sample to a concentration of 11.8%.
Method XI: The Method X reaction mixture was left at 65 ° C for an additional 44 minutes after sampling, cooled, and then diluted to 11.8% w / w in a 20 g / l NaOH solution.
Method XII: A mixture of the surfactant, the amine binder and the DMSO was stirred and heated to 65 ° C. The epoxy binder was slowly added to the mixture and then left for 2 hr and 2 min in total at 65 ° C. The glycidoxypropyltrimethoxysilane was then slowly added to the mixture. After 20 min, a sample of the reaction mixture was taken and slowly added to a stirred solution of NaOH 20 g / L, diluting the sample to a concentration of 11.8%.
Method XIII: The Method XII reaction mixture was left at 65 ° C for a further 40 minutes after sampling, cooled and then diluted to 11.8% w / w in a 20 g / l NaOH solution.
Results: Test 1 Bottle test method
Evaluation of the inhibition of DSP formation used similar test conditions to those used and previously published. To a stirred sample of the vegetable waste liquor, a small volume of the concentrated solution of sodium metasilicate pentahydrate was slowly added to increase the amount of silica in the liquor (typically, the concentration was increased by about 1 g / L as SiO2). This fortified liquor was then divided into 500 ml batches for treatment by adding the appropriate inhibitor at the desired dose. A batch of fortified liquor was kept as raw liquor.
Each of the treated batches was then subsampled to obtain duplicate samples which were individually placed in 250 ml Nalgene polypropylene bottles and placed in a rotating 95 ° C water bath. Untreated duplicate control samples were also included. After heating for 3 hours, the bottles were removed from the bath and the solids were collected by filtration, washed with hot water, and oven dried at 110 ° C. After drying, the resulting mass of precipitated DSP solids was weighed. The efficacy of the treatment was determined by comparing the precipitated DSP mass of the individual treated samples with the untreated control samples in the same test.
The results are presented as a percentage calculated as: (Average treated mass / Average untreated mass) x 100. A value of 100% means that there is no effective inhibition (the same mass as untreated) while a value less than 100% indicates some inhibitory activity. Lower numbers indicate more effective inhibition.
Type 1.1 Ethoxylated Alcohol / Siloxane Surfactant (not according to the invention as currently claimed)
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Table 1:% sodalite precipitate
<td rowspan="2">Product</td><td colspan="3">Dose (ppm)</td>
<td> 80</td><td> 120</td><td> 160</td>
<td>TO</td><td> 88</td><td> 75</td><td></td>
<td>TO*</td><td> 78</td><td> 73</td><td></td>
<td>TO*</td><td> 66</td><td></td><td> 57</td>
<td>B</td><td> 72</td><td></td><td> 61</td>
<td>C</td><td> 72</td><td></td><td> 61</td>
<td>D</td><td> 69</td><td> 45</td><td></td>
<td>AND</td><td> 70</td><td> 61</td><td> 61</td>
* repeated test under the same test conditions as above
Type 1.2 Ethoxylated Amine / Siloxane Surfactant (not according to the invention as currently claimed)
Table 2:% sodalite precipitate
<td rowspan="2">Product</td><td colspan="3">Dose (ppm</td><td colspan="2"></td>
<td> 80</td><td> 120</td><td> 160</td><td> 200</td><td> 220</td>
<td>F</td><td> 77</td><td> 91</td><td></td><td></td><td></td>
<td>G</td><td> 6</td><td></td><td> 0,6</td><td></td><td></td>
<td>H</td><td> 16</td><td></td><td> 2</td><td></td><td></td>
<td>H *</td><td> 8</td><td></td><td> 2</td><td></td><td> 1</td>
<td>H *</td><td> 11</td><td></td><td> 2</td><td></td><td> 0,8</td>
<td>J</td><td> 91</td><td></td><td> 58</td><td></td><td></td>
<td>K</td><td> 36</td><td></td><td> 11</td><td></td><td></td>
<td>L</td><td> 17</td><td></td><td> 4</td><td></td><td></td>
<td>M</td><td> 23</td><td> 6</td><td></td><td></td><td></td>
<td>M *</td><td> 28</td><td></td><td> 5</td><td> 4</td><td></td>
<td>M *</td><td> 25</td><td></td><td> 6</td><td></td><td></td>
<td>N</td><td> 27</td><td></td><td> 7</td><td></td><td></td>
<td>OR</td><td> 30</td><td></td><td> 4</td><td></td><td></td>
* repeated test under the same test conditions as above
Type 1.3 Fatty Amine / Siloxane Surfactant (not according to the invention as currently claimed)
Table 3:% sodalite precipitate
<td>Product</td><td colspan="3">Dose (ppm)</td>
<td></td><td> 40</td><td> 80</td><td> 120</td>
<td>P</td><td> 59</td><td> 16</td><td> 7</td>
<td>Q</td><td> 43</td><td> 58</td><td> 48</td>
Type 2.1 Ethoxylated Amine / Siloxane / Hydrophobic Surfactant (not according to the invention as currently claimed)
ES 2 835 705 T3
Table 4:% sodalite precipitate
<td rowspan="2">Product</td><td colspan="2">Dose (ppm)</td>
<td> 80</td><td> 120</td>
<td>R</td><td> 95</td><td> 101</td>
<td>S</td><td> 71</td><td> 81</td>
<td>T</td><td> 33</td><td> 9</td>
<td>T *</td><td> 32</td><td> 6</td>
* repeated test under the same conditions as the previous one
Type 2.2 Fatty Amine / Siloxane / Hydrophobic Surfactant (not according to the invention as currently claimed)
Table 5:% sodalite precipitate
<td rowspan="2">Product</td><td colspan="3">Dose (ppm)</td>
<td> 40</td><td> 80</td><td> 120</td>
<td>OR</td><td></td><td> 13</td><td> 9</td>
<td>OR*</td><td> 56</td><td> 28</td><td> 7</td>
<td>V</td><td></td><td> 86</td><td> 72</td>
<td colspan="4">* repeated test under the same conditions as the previous one</td>
Type 3.1 Fatty Amine Surfactant / Siloxane / Epoxy Binder (not according to the invention as currently claimed)
Table 6:% sodalite precipitate
<td rowspan="2">Product</td><td colspan="6">Dose (ppm)</td>
<td> 20</td><td> 40</td><td> 80</td><td> 100</td><td> 120</td><td> 140</td>
<td>X</td><td></td><td> 37</td><td> 3</td><td></td><td> 1</td><td></td>
<td>Y</td><td></td><td> 22</td><td> 4</td><td></td><td> 0,2</td><td></td>
<td>Y*</td><td> 58</td><td> 28</td><td> 13</td><td> 8</td><td> 4</td><td> 3</td>
<td>Y*</td><td></td><td> 15</td><td> 1,5</td><td></td><td></td><td> 0,4</td>
<td>Z</td><td></td><td> 27</td><td> 13</td><td></td><td> 5</td><td></td>
<td>ZA</td><td></td><td> 52</td><td> 3</td><td></td><td> 3</td><td></td>
* repeated test under the same conditions as the previous tests
Type 4.1 Fatty Amine Surfactant / Siloxane / Amine Binder / Epoxy Binder
ES 2 835 705 T3
Table 7:% sodalite precipitate
<td rowspan="2">Product</td><td colspan="4">Dose (ppm</td><td colspan="2"></td>
<td> 10</td><td> 20</td><td> 40</td><td> 60</td><td> 80</td><td> 140</td>
<td>AA</td><td></td><td></td><td> 57</td><td></td><td> 11</td><td> 4</td>
<td>BB</td><td></td><td></td><td> 25</td><td></td><td> 4</td><td> 0,1</td>
<td>DC</td><td></td><td></td><td> 78</td><td></td><td> 45</td><td> 0,7</td>
<td>DD</td><td></td><td></td><td> 12</td><td></td><td> 0</td><td> 0</td>
<td>DD *</td><td> 90</td><td> 73</td><td> 18</td><td> 0</td><td> 0</td><td></td>
<td>EE</td><td></td><td></td><td> 84</td><td></td><td> 59</td><td> 9</td>
<td>FF</td><td></td><td></td><td> 49</td><td></td><td> 0</td><td> 0</td>
<td>FF *</td><td> 93</td><td> 85</td><td> 46</td><td> 9</td><td> 0</td><td></td>
* repeated test under the same conditions as the previous one
Results: Test 2 Bottle test method
The conditions of Test 2 were similar to those of Test 1 but were designed to evaluate the effect on the initial formation of the DSP solids from the solution. As a result, a shorter retention time for the precipitation step and an increased initial concentration (highest peak) of silica in the liquor were used in this method. The data is presented again as a percentage of the precipitated mass compared to an undosed control sample.
Type 4.2 Fatty Amine Surfactant / Siloxane / Pentamine Binder / Epoxy Binder
Table 8:% sodalite precipitate
<td rowspan="2">Product</td><td colspan="3">Dose (ppm)</td>
<td> 25</td><td> 45</td><td> 50</td>
<td>JJ</td><td></td><td> 36</td><td></td>
<td>DS</td><td> 40</td><td></td><td> 0</td>
<td>IT IS</td><td> 18</td><td></td><td> 0</td>
<td>FS</td><td> 55</td><td></td><td> 24</td>
<td>GS</td><td> 50</td><td></td><td> 12</td>
ES 2 835 705 T3
Table 9:% sodalite precipitate
<td rowspan="2">Product</td><td colspan="6">Dose (</td><td colspan="5">ppm)</td>
<td> 20</td><td> 25</td><td> 30</td><td> 40</td><td> 45</td><td> 50</td><td> 60</td><td> 80</td><td> 100</td><td> 200</td><td> 400</td>
<td>SA</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 71</td><td> 62</td><td></td>
<td>SB</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 41</td><td> 1,8</td><td> 1</td>
<td>SC</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 36</td><td> 2,5</td>
<td>SD</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 59</td><td> 7</td>
<td>I KNOW</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 23</td><td> 3,4</td>
<td>SF</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 12,8</td><td> 2,3</td>
<td>SG</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 45</td><td> 0</td>
<td>SH</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 78</td><td> 57</td><td></td>
<td>YES</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 0</td><td> 0</td>
<td>SJ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 26</td><td> 0,3</td>
<td>SK</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 70</td><td> 27</td>
<td>SL</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 7</td><td> 2</td>
<td>YE</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 77</td><td> 0</td><td> 0</td>
<td>YN</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 156</td><td> 37</td>
<td>SW</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 24</td><td> 14</td><td></td>
<td>SP</td><td></td><td></td><td></td><td> 97</td><td></td><td></td><td> 77</td><td></td><td> 3,6</td><td> 0</td><td></td>
<td>SQ</td><td></td><td></td><td></td><td> 82</td><td></td><td></td><td> 62</td><td></td><td> 1,5</td><td> 0</td><td></td>
<td>MR</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 69</td><td> 28</td><td></td>
<td>ST</td><td></td><td></td><td></td><td> 78</td><td></td><td></td><td> 33</td><td></td><td> 2</td><td> 0</td><td></td>
<td>ITS</td><td></td><td></td><td></td><td> 74</td><td></td><td></td><td> 77</td><td></td><td> 0</td><td> 0</td><td></td>
<td>SV</td><td></td><td></td><td></td><td></td><td></td><td></td><td> 30</td><td> 4</td><td></td><td></td><td></td>
<td>SW</td><td></td><td></td><td> 56</td><td></td><td> 27</td><td></td><td> 0,5</td><td></td><td></td><td></td><td></td>
<td>SX</td><td></td><td></td><td></td><td></td><td></td><td></td><td> 41</td><td> 2</td><td></td><td></td><td></td>
<td>ACE</td><td></td><td> 70</td><td></td><td></td><td></td><td> 12</td><td></td><td></td><td></td><td></td><td></td>
<td>BS</td><td></td><td> 40</td><td></td><td></td><td></td><td> 3,3</td><td></td><td></td><td></td><td></td><td></td>
<td>CS</td><td></td><td> 32</td><td></td><td></td><td></td><td> 0</td><td></td><td></td><td></td><td></td><td></td>
<td>DS</td><td></td><td> 40</td><td></td><td></td><td></td><td> 0</td><td></td><td></td><td></td><td></td><td></td>
<td>IT IS</td><td></td><td> 18</td><td></td><td></td><td></td><td> 0</td><td></td><td></td><td></td><td></td><td></td>
<td>FS</td><td></td><td> 55</td><td></td><td></td><td></td><td> 24</td><td></td><td></td><td></td><td></td><td></td>
<td>GS</td><td></td><td> 50</td><td></td><td></td><td></td><td> 12</td><td></td><td></td><td></td><td></td><td></td>
<td>HS</td><td> 31</td><td></td><td></td><td> 0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
Type 4.3 Fatty Monoamine Surfactant / Siloxane / Pentamine Binder / Epoxy Binder
Table 10:% sodalite precipitate
<td rowspan="2">Product</td><td colspan="2">Dose (ppm)</td>
<td> 20</td><td> 40</td>
<td>LL</td><td> 44</td><td> 42</td>
<td>MM</td><td> 47</td><td> 41</td>
Test 2 - Surfactant-based molecules vs. Gen2 and Gen 3
ES 2 835 705 T3
Table 11:% sodalite precipitate
<td rowspan="2">Product</td><td></td><td></td><td></td><td></td><td></td><td>Dose</td><td>ppm)</td><td></td><td></td><td></td><td></td>
<td> 20</td><td> 25</td><td> 30</td><td> 50</td><td> 100</td><td> 200</td><td> 400</td><td> 500</td><td> 800</td><td> 1100</td><td> 1200</td>
<td>Gen2</td><td></td><td></td><td></td><td> 106</td><td> 114</td><td> 76</td><td></td><td> 39</td><td> 40</td><td> 37</td><td></td>
<td>Gen3</td><td></td><td></td><td></td><td> 88</td><td> 92</td><td> 81</td><td> 55</td><td></td><td> 32</td><td></td><td> 32</td>
<td>DD</td><td></td><td></td><td></td><td> 103</td><td> 79</td><td> 41</td><td> 1</td><td></td><td></td><td></td><td></td>
<td>HS</td><td> 58</td><td> 16</td><td> 0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
The results in Table 11 above demonstrate the striking difference between the inhibitory effects of previously identified small molecule inhibitors (Gen 2 and Gen 3 products) and surfactant-based products (DD and HS). The latter are effective in eliminating DSP formation at doses as low as 30 ppm. However, for Gen2 and Gen 3 products, some precipitation of DSP still occurs under these test conditions, even at doses above 1000 ppm. Given the efficacy of the Gen 2 and Gen 3 products under the conditions of Trial 1, such a result is unexpected and novel.
Results: Test 3 - Metallic Coupon Test
The conditions of Test 3 were the same as those of Test 2, however, metal coupons were included in the bottles and small amounts of the DSP precipitated on the metal surface. As shown in Figure 6, SEM analysis of coupon tests using the invention shows that significant amounts of the DSP precipitated on the untreated coupon, as well as on those treated with extreme doses (1000 ppm) of GEN2 products. and GEN3. However, in the coupon subjected to the liquor treated with the surfactant-based inhibitor (KK) at a relatively low dose (100 ppm), significantly less DSP was deposited. This indicates a surprising and substantial efficacy of the surfactant-based small molecule in inhibiting the formation of DSP scale.
Table 2.15 Treatment of liquor exposed to metal coupons in test method 3.
<td>Coupon</td><td>kind of product</td><td>Product</td><td>Dose (ppm)</td>
<td>I</td><td>No treatment</td><td>N / A</td><td>N / A</td>
<td>II</td><td>Product Type D</td><td>GEN2</td><td> 1000</td>
<td>III</td><td>Product Type E</td><td>GEN3</td><td> 1000</td>
<td>IV</td><td>Product Type 4.2</td><td>KK</td><td> 100</td>
Contents15
16 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16
72 members in 11 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 201414151368 | United States of America | A | |
| 201414151368 | United States of America | A | |
| 201414151368 | United States of America | – | |
| 2014073050 | United States of America | W | |
| 2014073050 | United States of America | W | |
| 201414151368 | – | – | – |
| PCTUS2014073050 | – | – | – |
| US201414151368 | – | – | – |
| WO2014US73050 | – | – | – |
Members72
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| US2011076209A1 | United States of America | A1 | |
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| RU2012109212A | Russian Federation | A | |
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| EP2678343A2 | European Patent Office (EPO) | A2 | |
| US2014124451A1 | United States of America | A1 | |
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| EP2678343A4 | European Patent Office (EPO) | A4 | |
| AU2014376173A1 | Australia | A1 | |
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| US9416020B2 | United States of America | B2 | |
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| AU2013222328B2 | Australia | B2 | |
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| ES2835705T3This record | Spain | T3 | |
| EP2678343B1 | European Patent Office (EPO) | B1 | |
| BR112016015920B1 | Brazil | B1 | |
| ES2895726T3 | Spain | T3 | |
| CA2935948C | Canada | C |
Numbers
- Publication
- 2835705
- Publication, DOCDB
- 2835705
- Publication, EPODOC
- ES2835705T
- Application
- 14878084
- Application, DOCDB
- 14878084
- Application, EPODOC
- ES20140878084T
Titles2
- Spanish
- Moléculas pequeñas basadas en tensioactivos para reducir la incrustación del aluminosilicato en el proceso de Bayer
- English
- Small molecules based on surfactants to reduce the scaling of the aluminosilicate in the Bayer process
Classification
- CPC, 3
- C01F7/0633
- C01F7/00
- C01F7/06
- IPC, 3
- C01F7 00
- C01F7 06
- C01F7 0633