EA040865B1 - COMPOSITIONS AND METHODS FOR IMPROVING THE PRODUCTION OF ALUMINUM HYDROXIDE IN THE PROCESS OF PRODUCING ALUMINUM HYDROXIDE - Google Patents

Description

Cross-reference to related applications

The present application claims priority on the basis of U.S. Provisional Application No.

14/619979, filed February 11, 2015, the contents of which are incorporated herein in their entirety by reference.

Federally funded research or development statement

Not applicable

Technical field

The invention relates to compositions and methods used as crystal growth modifiers (CGM) in the Bayer process. Compositions of CGM contain a component containing unrefined corn oil obtained during the production of bioethanol, and/or a biodiesel component. CGM compositions can be used to modify the particle size and distribution of precipitated aluminum hydroxide during crystallization in the precipitation solution.

State of the art

Aluminum is the most widely used non-ferrous metal. Although it is one of the most common elements, pure aluminum is rare. In fact, primary aluminum is obtained from alumina (Al ₂ O ₃ ), the so-called alumina. In general, aluminum oxide is produced or extracted from aluminum ores, in particular bauxite. Aluminum ores contain other materials such as silica, various iron oxides and titanium dioxide that must be separated from alumina. After separation of aluminum oxide from these materials, it can be refined to produce aluminum metal. The separation of aluminum from these materials represents the largest individual cost step.

Typically, aluminum is separated from other materials present in the ore using the Bayer process. The Bayer process includes a series of successive stages: leaching, purification, precipitation, classification and calcination. In the leaching stage, alumina is recovered by leaching bauxite ore with sodium hydroxide solution at high pressure and temperature. As a result, sodium aluminate is formed. In the purification stage, the solid phase residue, the so-called red mud, is removed from the sodium aluminate into solution. In the precipitation step, crystals of aluminum hydroxide (Al(OH) ₃ ) are precipitated from the sodium aluminate solution. The growth of these crystals is facilitated by the use of small particles of aluminum hydroxide, the so-called nuclei. These nuclei provide adhesion surfaces on which crystals form and grow. At the classification stage, crystals and nuclei are separated from the production solution. Finally, in the calcination step, aluminum hydroxide decomposes to alumina, the end product of alumina.

Strict control of the size of the formed crystals at the stage of deposition leads to an increase in the overall yield of aluminum hydroxide. Therefore, the operator must carefully control operating parameters such as deposition temperature and cooling rate. The specific crystal sizes are ideal for fast and efficient separation from solution and subsequent processing. Other crystal sizes are ideal for use as future seeds.

Serious efforts are being made to find chemical additives and ways to control the size of the crystals produced during precipitation. Such attempts include the addition of crystal growth modifiers (CGM) during the precipitation step. However, there is still a need to improve and optimize the aluminum hydroxide production process in order to improve product quality and economic performance.

The information set forth in this section is not intended to represent facts that are referred to in any patent, publication or other sources of information as prior art in relation to this invention, unless otherwise specifically noted. In addition, this section should not be taken as an indication that research has been done or that other relevant information is missing as defined in 37 CFR § 1.56(a).

The essence of the invention

To meet the needs of the industry developed compositions and methods related to the modification of the crystallization of aluminum hydroxide in the production of aluminum hydroxide, such as the Bayer process. In at least one embodiment, the present invention relates to crystal growth modifier (CGM) compositions and their addition to the precipitation solution of the crystallization process to, in at least some embodiments, optimize the production of crystalline agglomerates from the precipitation solution of the crystallization process.

In some embodiments of the invention, CGM compositions for optimizing the production of crystalline agglomerates from the precipitation solution of the crystallization process contain a component containing unrefined corn oil, a biodiesel component, or mixtures thereof. The component containing unrefined corn oil contains unrefined corn oil recovered as a separate phase by-product of the ethanol production process, containing monoalkyl esters, including ethyl esters of C ₁₆ and C ₁₈ acids, esters of diglycerol and triglycerol of long-chain fatty acids. acids and may contain free fatty acids. The biodiesel component contains one or more long chain fatty acid methyl ester-containing biodiesels, including C ₁₆ and C ₁₈ acid methyl esters, and may contain free fatty acids. In some embodiments, CGM compositions may be substantially free of additional components.

In some embodiments, the implementation of the CGM contains: 1-100 wt.% component representing unrefined corn oil, biodiesel component, or a mixture thereof; and 0-99% by weight of a carrier fluid, which may contain a hydrocarbon fluid. The crude corn oil component contains crude corn oil recovered as a phased by-product of the ethanol production process, and the biodiesel component contains biodiesel substantially containing long chain fatty acid methyl esters.

The crude corn oil component may contain 80 wt.% or more, and in some embodiments, 85 wt.% or more monoalkyl esters, including ethyl esters of C ₁₆ and C ₁₈ acids, diglycerol and triglycerol esters of long chain fatty acids, and may contain 0-15 wt.% free fatty acids. In some embodiments, the crude corn oil component may comprise ethyl esters of C ₁₆ and C ₁₈ acids from crude corn oil in an amount of 1-10 wt.% and esters of diglycerol and triglycerol in an amount of 50-95 wt.%. In some embodiments, the crude corn oil containing component contains 1-10% by weight of C ₁₆ -C ₁₈ ethyl esters; 0.2-8 wt.% diglycerol esters; and 70-90 wt.% triglycerol esters. Free fatty acids may be present in varying amounts from the range of 0-15% by weight.

Compositions of CGM containing a component containing unrefined corn oil may contain this component in amounts in the range of 1-100 wt.%. In other exemplary embodiments, the unrefined corn oil containing component contains it in amounts of 40-100% by weight and 98-100% by weight. In some embodiments, the CGM compositions may contain 0.01-10% by weight of C ₁₆ -C ₁₈ acid ethyl esters and, in some embodiments, 0.5-95% by weight of diglycerol and/or triglycerol esters.

The biodiesel component essentially contains methyl esters of long chain fatty acids. In some embodiments, the biodiesel component contains 90 wt. % or more of C ₁₆ , C ₁₈ or C ₂₂ acid methyl esters and 0-2 wt. % free fatty acids. In other embodiments, the biodiesel component contains methyl esters of C ₁₆ , C ₁₈ or C ₂₂ acids in amounts of 96 wt.% or more and 98 wt.% or more. In some embodiments, the biodiesel component comprises biodiesel derived from soybeans and/or rapeseed.

In some embodiments of the invention, methods are disclosed for optimizing the production and recovery of crystalline agglomerates from the precipitation solution of a crystallization process using the embodiment of CGM compositions described herein. In some embodiments, the method includes the following steps:

(i) a step in which the CGM composition is added to the precipitation solution in an amount sufficient to increase the particle size of the crystalline agglomerates;

(ii) a step in which the CGM composition is distributed over the precipitation solution; and (iii) a step in which the crystalline agglomerates are precipitated from the precipitation solution.

The addition of the CGM composition results in an increase in the particle size of the recoverable crystalline agglomerates compared to the process of crystallization in the precipitation solution in the absence of a crystal growth modifier.

The benefits of the compositions and methods of the present invention include, but are not limited to: reducing costs associated with the aluminum hydroxide production process while improving the efficiency and effectiveness of the aluminum hydroxide production process. Benefits further include generating low cost raw materials for CGM products and methods for formulating such CGM products. In addition, the benefits further include generating CGM feedstock that can be used in the production of high quality aluminum hydroxide, which can be used to produce high quality aluminum, as well as minimizing or reducing environmental impact. Additional benefits include the ability to dispose of a by-product that is otherwise regarded as waste, as well as the minimization or reduction of harmful environmental impacts associated with this disposal.

The above summary of the various aspects of the disclosure is not intended to describe every illustrated aspect or every embodiment. While many embodiments have been disclosed, other features, embodiments, and advantages of the present invention will be apparent to those skilled in the art from the detailed description below,

- 2 040865 which shows and describes illustrative embodiments of the invention.

Accordingly, the detailed description is to be taken as illustrative in nature and not restrictive.

Detailed description of the invention

Below are definitions of significant terms that are used in this description. The wording of the definitions is provided for convenience only and is not intended to limit any of the definitions to any particular category.

A/C denotes the ratio of alumina to caustic.

CGM stands for crystal growth modifier.

Biodiesel refers to monoalkyl esters of long chain fatty acids derived from vegetable oils or animal fats.

Hydrocyclone refers to a device used to classify, separate or sort particles in a liquid suspension based on the ratio of their centripetal force to the resistance of the liquid. Hydrocyclones are typically used to separate dense and large particles from light and small particles. Hydrocyclones often have a cylindrical section on top with a tangential liquid supply and a conical base. Hydrocyclones often have two drains on the axis: a smaller one at the bottom (for the bottom product) and a larger one at the top (for the top product). In general, the bottom product is the denser or coarser fraction, while the top product is the lighter or finer fraction.

Mass fraction in percent means the total weight of the fraction of one reagent in 100 g of the composition or mixture.

Product yield refers to the amount of aluminum hydroxide solids in the settling chamber at the end of the settling cycle. An increase in product yield is usually indicated by a lower concentration of aluminum hydroxide in the corresponding chamber solution.

A solution or Bayer solution refers to a caustic, liquid medium that is used in at least a portion of a Bayer process line at an industrial facility.

Precipitating solution means a solution containing aluminate present in the aluminum hydroxide precipitation step in alumina production. The aluminate solution may be referred to by various terms known to those of ordinary skill in the art, such as mother liquor, aluminate liquor, and aluminum hydroxide precipitation feedstock.

Precipitation raw material solution refers to the precipitation solution that flows into the precipitation apparatus in the aluminum hydroxide precipitation process.

A thickener or settling tank refers to a vessel that is used to separate a slurry into solid and liquid phases, often with the addition of flocculants. The container may be designed and adapted to receive the slurry, hold it for a period of time sufficient to allow the solid portions of the slurry (bottom) to settle down away from the more liquid portion of the slurry (top), drain the top and remove the bottom. The bottoms thickener and the tops thickener often pass to filters to further separate solids from liquids.

Waste liquor refers to the liquor resulting from the removal of precipitated aluminum after the final classification step. It is often recycled back to be leached in the Bayer process.

The bioethanol process refers to a process for the production of ethanol or ethyl alcohol from starch or sugar-containing feedstock by either wet milling or dry milling.

The wet milling process refers to the process used in the Bioethanol Process to convert corn into ethanol. In the wet milling process, corn kernels or seeds are slurried in warm water and dilute acid. After being turned into a suspension, proteins are destroyed and starch is released. The slurry is processed (milled) through a series of mills to separate the corn germ and fibers from the starch. Unrefined corn oil is extracted from the germ as a by-product. Starch is used to produce ethanol. The remaining proteins, fat, fiber and other nutrients can be sent to the global livestock and poultry feed markets, or they can be used for other known purposes.

In the event that the above definitions or the description provided elsewhere in this application are inconsistent with the commonly used meanings (explicitly or implicitly) presented in the dictionary or given in the source introduced into this application by reference, the terms in the application and the claims in in particular should be understood as being interpreted in accordance with the definition or description given in this application, and not in accordance with the usual definition, dictionary definition or definition that has been introduced by reference. In light of the foregoing, in the case where a term can only be understood if interpreted by a dictionary, if the definition of the term appears in the Kirk-Othmer Encyclopedia of Chemical Technology, ^5th Edition, (2005), (Published by Wiley, John & Sons, Inc. ), this definition shall govern the interpretation of the term in the claims.

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While the invention is capable of being embodied in many different forms, this disclosure will describe embodiments of the invention in detail, with the understanding that the present disclosure is to be considered as illustrative examples of the principles of the invention, and that it is not intended to limit the scope of the invention to the illustrated embodiments.

At least one embodiment of the invention relates to a CGM composition. In at least one embodiment, the CGM composition is added to the precipitation solution in a Bayer process system. This CGM composition enhances aluminum recovery by increasing the particle size of the aluminum hydroxide crystals. The CGM composition contains a component containing unrefined corn oil, a biodiesel component, or mixtures thereof. In some embodiments, the CGM composition may further comprise a carrier fluid. In other embodiments, the CGM composition may further comprise a fatty acid component comprising a fatty acid or mixture of fatty acids having a C ₈ -C| ₀ carbons. Later in this document, the components of embodiments of the CGM composition and methods of its use are described.

Component containing unrefined corn oil

The crude corn oil component contains, and in some embodiments, consists essentially of various phases released during the bioethanol process with the corn feedstock. In the corn feed bioethanol process, corn is converted into ethanol. In at least one embodiment, wet milling is used in the bioethanol process.

Unrefined corn oil contains monoalkyl esters, diglycerol and triglycerol esters of long chain fatty acids, free fatty acids, and other components. Fatty acid monoalkyl esters contain ethyl esters of C16-C18 acids of the following formula:

Iy δ

I ..... C - C- ¢n n \ in some embodiments, R denotes C ₁₅ -C ₁₇ (corresponding to ethyl esters of acids C ₁₆ -C ₁₈ ). In some embodiments, the C ₁₆ -C ₁₈ ethyl ester fatty acid chains may include saturated fatty acid chains and unsaturated fatty acid chains. In some embodiments, the C ₁₆ -C ₁₈ fatty acid chains of the ethyl esters were straight chain.

Examples of suitable ingredients containing crude corn oil include crude corn oil by-product having at least 1% by weight of C ₁₆ -C ₁₈ ethyl esters; 1.5-10 wt.% complex ethyl esters of acids C ₁₆ -C ₁₈ ; and 1.5-8 wt.% complex ethyl esters With ₁₆ -C ₁₈ . Examples of suitable unrefined corn oil derived from, or a by-product of, the corn bioethanol process may include the following components: base components containing C16:0 ethyl ester, C16:0 acid, C18:2 ethyl ester, C18 :2 acid; C18:1 ethyl ester, C18:1 acid; C18:0 ethyl ester, C18:0 acid; fatty acid monoglycerol ester (MG); fatty acid diglycerol ester (DG); triglycerol fatty acid ester (TG); and some sterols, eg stigmasterol, sitosterol, methylcholesterol; minor components including tocopherol, squalene, C16:1 ethyl ester, C16:1 acid, C14:0 ethyl ester, C14:0 acid; and additional minor components may include C12:0 acid, C10:0 acid, myo-inositol, C4:0 acid, C5:0 acid, 1,3-butanediol, 1,3-propanediol, succinic acid, and the like.

Typical examples of constituents of by-product samples of unrefined corn oil are shown in Table 1. I. In the table. I presents the constituents of samples of a commercially available by-product unrefined corn oil, which were determined by gas chromatography-mass spectrometry (GC-MS) and were quantified by high-temperature gas chromatography-flame ionization (GC-FID) with C21:0 acid in as an internal standard.

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Table I. Components Sample Ethyl ester Fatty acid Fatty acid monoglycerol ester Sterol Difficult fatty acid diglycerol ester Fatty acid triglycerol ester other Total 1 2.63% 12.43% 0.84% 1.08% 5.62% 77.06% 0.36% 100.00% 2 2.13% 12.81% 0.53% 0.64% 6.08% 77.80% 0.00% 100.00% 3 1.92% 10.59% 0.77% 0.29% 0.31% 86.12% 0.00% 100.00% 4 7.66% 4.03% 0.71% 0.40% 3.43% 83.77% 0.00% 100.00% 5 1.91% 10.65% 0.70% 0.20% 2.11% 84.42% 0.00% 100.00% 6 3.17% 10.10% 0.69% 0.40% 3.37% 82.28% 0.00% 100.00% 7 5.59% 8.92% 0.90% 0.81% 4.41% 79.37% 0.00% 100.00%

Each sample (1-7) is from different quantities of a commercially available crude corn oil by-product purchased from various bioethanol suppliers in the United States.

States of America.

In some embodiments, the crude corn oil component may contain C ₁₆ -C ₁₈ ethyl esters and diglycerol and triglycerol esters in amounts of 80 wt.% or more and 85 wt.% or more. In some embodiments, C ₁₆ -C ₁₈ ethyl esters comprise 1-10% by weight of the crude corn oil containing component. The amount of esters of diglycerols and triglycerols can be 50-95 wt.% component containing unrefined corn oil. Further, in some embodiments, the crude corn oil containing component contains 1-10% by weight of C ₁₆ -C ₁₈ ethyl esters; 0.2-8 wt.% diglycerol esters; and 70-90 wt.% triglycerol esters.

In at least one embodiment, the crude corn oil containing component contains free fatty acids in an amount of 0-15% by weight. Embodiments of the invention may contain various amounts of free fatty acids, including, but not limited to, 0-10 wt.%, 1-14 wt.%, 3-14 wt.%, 4-15 wt.% and 10-15 wt. .%.

biodiesel component

The biodiesel component contains and, in some embodiments, consists essentially of biodiesel or blends of biodiesels. The biodiesel(s) contain long chain fatty acid monoalkyl esters and may contain free fatty acids. Examples of suitable biodiesels and their constituents include, but are not limited to, one, more or all of the components listed in Table. II.

Table II. Examples of biodiesel compositions. Components (wt%) (all methyl esters)

Oily or greasy type C8:0 С10:0 C12:0 C14:0 С16:0 С18:0 S20:0 C22:0 С24:0 S18:1 C22:1 S18:2 S18:3 Total Soya beans 0 0 0 0.1 10.3 4.7 0 0 0 22.5 0 54.1 8.3 100 rape seeds 0 0 0 0 2.7 2.8 0 0 0 21.9 50.9 13.1 8.6 100 beef lard 0 0.1 0.1 3.3 25.2 19.2 0 0 0 48.9 0 2.7 0.5 100 Peanut 0 0 0 0 10.4 8.9 0 0 0 47.1 0.2 32.9 0.5 100 Canola 0 0 0 0.1 3.9 3.1 0 0 0 60.2 0.5 21.1 I,1 100 Olives 0 0 0 0 AND 3.6 0 0 0 75.3 0 9.5 0.6 100 coconuts 8.3 6 46.7 18.3 9.2 2.9 0 0 0 6.9 0 1.7 0 100 Corn 0 0 0 0 9.9 3.1 0 0 0 29.1 0 56.8 1.1 100 palm trees OD 0.1 0.9 1.3 43.9 4.9 0 0 0 39 0 9.5 0.3 100 safflower 0 0 0 0.1 6.6 3.3 0 0 0 14.4 0 75.5 0.1 100 Sunflower 0 0 0 0.1 6 5.9 0 0 0 16 0 71.4 0.6 100 Sanola 0 0 0 0 3 4.4 0 0 0 88.2 0 4.3 0.1 100 Cow butter fat 5.5 3 3.6 11.6 33.4 I,4 0 0 0 27.8 0 3.1 0.6 100 Lard 0 0.1 0.1 1.4 25.5 15.8 0 0 0 47.1 0 8.9 1.1 100 cottonseed 0 0 0 0.8 22.9 3.1 0 0 0 18.5 0 54.2 0.5 100 Crambe 0 0 0 0 2.07 0.7 2.09 0.8 1.12 18.86 58.51 9 6.85 100 Flax-seed 0 0 0 0 4.92 2.41 0 0 0 19.7 0 18.03 54.94 100 Safflower N.O. 0 0 0 0.34 5.46 1.75 0.23 0 0 79.36 0 12.86 0 100 Sesame 0 0 0 0 13.1 3.92 0 0 0 52.84 0 30.14 0 100

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Additional details on biodiesels, biodiesel components and methyl esters from biodiesel are provided in Sanford, S.D., et al., Feedstock and Biodiesel Characteristics Report, Renewable Energy.

The long chain fatty acid monoalkyl esters of the biodiesel(s) contain methyl esters. Methyl esters may have the following formula:

O “SK*’4 O

In some embodiments, R is C7-C21 (corresponding to C ₈ -C ₂₂ acid methyl esters). In some embodiments, R is C ₁₅ , C ₁₇ or C ₂₁ (corresponding to methyl esters of C ₁₆ , C ₁₈ or C ₂₂ acids). In at least one embodiment, C ₈ -C ₂₂ acid methyl esters comprise 80 to 98 wt % of the total methyl esters present. In some embodiments, the methyl ester fatty acid chains comprise saturated fatty acid chains. In some embodiments, the methyl ester fatty acid chains comprise unsaturated fatty acid chains. In some embodiments, the ethyl ester fatty acid chains were straight chain.

In at least one embodiment, the long chain fatty acid monoalkyl esters are methyl esters and contain up to and including 98% by weight or more of the biodiesel component. Free fatty acids may comprise up to and including 02% by weight or more of the biodiesel component.

In at least one embodiment, the biodiesel component comprises and may consist essentially of soybean biodiesel, rapeseed biodiesel, or mixtures thereof.

carrier fluid

In at least one embodiment, the CGM contains a carrier fluid. The carrier fluid may be a composition that allows the hydrolysis of some or all of the esters in biodiesel or raw corn oil containing components. The carrier fluid may be used alone or mixed in any proportion. The carrier fluid may be a solvent. The carrier fluid may have a boiling point that is safe enough to exceed the temperature of the hot aluminate solution in which precipitation occurs (about 80° C., 176° F.) in the Bayer process.

In at least one embodiment, the carrier fluid is a hydrocarbon carrier such as a hydrophobic fluid or mixtures of hydrophobic fluids. The hydrophobic liquid or mixtures of hydrophobic liquids may contain aliphatic or aromatic oil compounds. Suitable examples include: paraffin oils, naphthenic oils or fuel oils, or any mixture thereof. Examples of suitable hydrocarbon carriers include the oil carriers disclosed and described in US Pat. No. 4,737,352, which is incorporated herein by reference in its entirety.

In at least one embodiment, the hydrophobic liquid is an alcohol distillation residue. The alcohol distillation residue is a fatty alcohol-ether ester complex generated during the alcohol distillation process. These residues are formed as bottom or sedimentary wastes that remain during the production of aliphatic or alkyl alcohols, for example, C ₁₀ -C ₂₂ alcohol. An example of a suitable waste product is a Xiu alcohol distillation residue having a boiling point of about 250°C (482°F). It has a specific gravity of about 0.862, a number of OH groups of about 90, a weight percent of acetic acid groups of about 0.07, and a weight percent of carbonyl groups of about 0.5. In a chemical aspect, it consists of 57-73 wt.% C ₁₀ -C ₂₂ primary branched chain alcohols and 29-41 wt.% mixed long chain esters and ethers (C ₁₈ -C ₃₃ acid ester; C ₁₈ -C ₂₂ ).

In at least one embodiment, the carrier oil is a mixture of tall oil fatty acid mixed with a C ₁₀ alcohol distillate, naphthenic oil, and any combination thereof. The weight ratios of this mixture are within the range of 12:88 to 20:80, preferably 15:85. It can be administered in an amount between 15-25 mg/l, preferably 20 mg/l.

fatty acid component

In at least one embodiment, the fatty acid component comprises, and in some embodiments consists essentially of, a fatty acid or mixture of fatty acids having a C ₈ -C ₁₀ alkyl chain length of carbon atoms. In some embodiments, the C ₈ -C ₁₀ fatty acid has a non-functional, saturated, and unbranched carbon backbone.

Some examples of suitable fatty acids and mixtures thereof are described in US Pat. No. 7,955,589, which is incorporated herein by reference in its entirety. One example is a C ₈ -C ₁₀ fatty acid composition with an average molecular weight of 154 g/mol. The composition has the following distribution of fatty acid chain lengths: C ₆ < 6%, C ₈ 53-60%, C 34-42% and C ₁₂ < 2%.

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The carbon chain(s) may be saturated or unsaturated, branched or unbranched, and have no functional groups. Representative examples of this composition include the commercially available product C-810 supplied by Proctor and Gamble, which can be dispersed in a commercially available paraffinic hydrocarbon oil sold by ExxonMobil under the trade name ESCAID 110.

The C ₈ -C ₁₀ fatty acid may be dissolved in the carrier liquid (described below). An example includes a hydrocarbon oil with a boiling point greater than about 93.3°C (200°F). In some embodiments, the C ₈ -C ₁₀ fatty acid and hydrocarbon oil may have a weight ratio in the range of 12:88 to 20:80, preferably 15:85.

Composition

In at least one embodiment, the CGM compositions comprise or essentially consist of a crude corn oil containing component, a biodiesel component, or mixtures thereof. In some embodiments, the compositions may further comprise a carrier fluid. In some embodiments, the CGM compositions contain, and in some embodiments essentially consist of: 1) a crude corn oil containing component, a biodiesel component, or mixtures thereof; 2) carrier fluid; and 3) a fatty acid component. In the various embodiments described herein, the CGM compositions may not contain added water.

In cases where the CGM contains a component containing unrefined corn oil, in some embodiments, this component is 1-100 wt.% CGM. In various implementations, CGM contains a component containing unrefined corn oil, in the following amounts: 10-100 wt.%; 40-100 wt.%; 70-100 wt.% and 98-100 wt.%. In some embodiments, in cases where the CGM contains a component containing unrefined corn oil, ethyl esters of C ₁₆ -C ₁₈ acids can be 0.01-10 wt.% CGM and esters of diglycerol and triglycerol can be 0.5- 95 wt% CGM. In some embodiments, ethyl esters of C ₁₆ -C ₁₈ acids and esters of diglycerol and triglycerol may comprise 25 wt.% or more, 50 wt.% or more, or 85 wt.% or more CGM. Embodiments of the invention may include CGM compositions with deviations from the above amounts of the crude corn oil containing component, which distinguishes them from the crude corn oil compositions described above.

In cases where the CGM contains a biodiesel component, the biodiesel component may comprise 1.0-100% by weight of the CGM. In various implementations, CGM contains a biodiesel component in the following amounts: 10-100 wt.%; 40-100 wt.%; 70-100 wt.% and 98-100 wt.%. Embodiments of the invention may include CGM compositions with deviations from the above amounts of the biodiesel component, which distinguishes them from the biodiesel compositions described above.

In at least one embodiment, the CGM contains a blend of a crude corn oil containing component and a biodiesel component. The present disclosure includes any mixture of these two components in any ratio. Examples of CGMs containing a biodiesel component and a crude corn oil component include, but are not limited to, CGMs having blend ratios of 1-99:1-99, 10-90:10-90, 50:50, 25:75 and 75:25.

In at least one embodiment, the CGMs comprise or essentially consist of a crude corn oil containing component, a biodiesel component, or mixtures thereof. In at least one embodiment, CGM is used in its purest form. In at least one embodiment, the CGM formulation includes a dissolving component containing unrefined corn oil and/or a biodiesel component in a carrier fluid. The carrier fluid may comprise 35-85% by weight of the CGM composition. The present disclosure includes any mixture of a crude corn oil containing component, a biodiesel component, and a carrier fluid in any proportion.

Application of CGM compositions

In at least one embodiment, the mixed/prepared CGM composition is fed into the aluminate or mother liquor of the Bayer deposition process. The mixed CGM composition may be fed into the process in an amount sufficient to achieve the desired changes. In some embodiments, the compositions may be administered in their original form without further preparation.

The precipitation process in the Bayer process involves the formation of nuclei, the primary growth of crystals and the agglomeration of these crystals into coarse or sandy particles of aluminum hydroxide. Coarse or sandy particles of aluminum hydroxide are dried and often calcined to obtain Al ₂ O ₃ in the form of a commercial final product with commercial value.

The aluminate or mother liquor present in the settling stage of the Bayer process is the hot caustic liquor obtained after removal of the red mud. This aluminate solution contains dissolved sodium aluminate. Part of dissolved aluminate particles

- 7 040865 sodium is a fine material (eg -325 mesh or finer). The aluminate solution and, optionally, additional fine aluminum hydroxide particles are fed into a suitable settling tank or a series of associated tanks. In this case, the aluminate solution is cooled with stirring, which leads to the precipitation of aluminum hydroxide crystals on the nuclei. Although the growth of fairly large crystals is desirable, the complete exclusion of fine material is often not the most desirable result. The reason is that some of the remaining fine particles can be reused as seeds for future precipitation steps.

In at least one embodiment, the CGM composition is introduced into the precipitation solution via one or more routes. For example, a crystal growth modifier can be added by direct injection to the precipitation solution in the following steps of the Bayer process:

a) into the supplied precipitating solution,

b) into the germ suspension or other stream entering the settling tank,

c) directly into the settling tank and

d) a combination of these paths.

In some embodiments, the CGM composition is added such that it is evenly distributed in the Bayer settling medium for unhindered contact with fine particles. In at least one embodiment, the CGM is emulsified before being added to the precipitation solution.

In at least one embodiment, the amount of CGM added to the precipitation solution is proportional to the surface area of the aluminum hydroxide particles present. For example, CGM may be added in an amount in the range of about 0.01 to about 30 mg CGM/m ² available surface area of the aluminum hydroxide nuclei. In some embodiments, the amount may be in the range of about 0.1 to about 15 mg CGM/m ² available surface area of the aluminum hydroxide nuclei. In some other embodiments, an amount is used that may be less than about 8 mg CGM/m ² available surface area of the aluminum hydroxide nuclei. In some embodiments, the amount may be 1-3 mg CGM/m ² available surface area of the aluminum hydroxide nuclei.

In at least one embodiment, the dosage of added CGM is tied to the volume of solution to which it is added. This is especially useful in situations where the available aluminum hydroxide surface area cannot be determined reliably. The amount of CGM added may range from about 0.01 to about 400 mg CGM/L of precipitation solution. In at least one embodiment, the amount is in the range of about 0.05 to about 200 mg CGM/L of precipitation solution. In at least one embodiment, the amount may be less than about 100 mg CGM/L of precipitation solution. In at least one embodiment, the amount may be in the range of about 10 to about 40 mg CGM/L of precipitation solution.

Typical examples of methods for introducing a CGM formulation into a Bayer process include one or more of the methods described in US Pat. Nos. 8,784,509; 7,771,681; 7,976,820; The CGM formulation may be used in combination with one or more other agents related to the modification of aluminum hydroxide crystallization in alumina production processes, such as those described in: US Pat. No. 5,106,599; EP0465055E1; US patent 6599489; US patent 5312603; and US Patent 6,168,767.

The patents and publications mentioned and any others otherwise mentioned in this disclosure are incorporated herein in their entirety by reference. The methods, terms, equipment, materials, and ideas disclosed therein are incorporated herein only to the extent that they supplement or expand the understanding and scope of the embodiments and claims of the invention disclosed herein and do not conflict or appear to be inconsistent with such understanding and volume.

Applications and uses of manufactured alumina include, but are not limited to, the use of alumina in the production of aluminum metal, abrasives, plastic fillers, and catalyst supports for industrial catalysts.

Each of the components and methods disclosed herein may be used alone or in conjunction with other components and methods to create improved compositions and methods for making and using them. Therefore, the combinations of components and methods disclosed herein may not need to implement the disclosure in its broadest sense, and are instead disclosed simply to specifically describe various implementation options.

Some examples of embodiments of the invention include, but are not limited to:

1. Composition for optimizing the production of crystalline agglomerates from the precipitation solution of the crystallization process, containing: 1-100 wt.% component containing unrefined corn oil or biodiesel component, in which the component containing unrefined

- 8 040865 corn oil, contains unrefined corn oil recovered as a separated phase by-product of the ethanol production process, and in which the biodiesel component of the biodiesel component contains biodiesel containing methyl esters of long chain fatty acids; and 0-99 wt.% of the carrier fluid, and the carrier fluid contains a hydrocarbon liquid.

2. The composition according to embodiment 1, wherein the composition contains a component containing unrefined corn oil, and the component containing unrefined corn oil contains 80 wt.% or more complex monoalkyl esters, including ethyl esters of C ₁₆ and C ₁₈ acids, esters diglycerol and triglycerol esters of long chain fatty acids; and 0-15 wt.% free fatty acids.

3. The composition of embodiment 2, wherein the composition contains 40-100 wt.% of a component containing unrefined corn oil.

4. Composition according to embodiment 2, wherein the composition contains 98-100 wt.% of a component containing unrefined corn oil.

5. The composition of Embodiment 2, comprising a volume of carrier fluid, wherein the hydrocarbon fluid is a hydrocarbon oil containing aliphatic or aromatic oil compounds selected from the group consisting of paraffin oils, naphthenic oils, mixed paraffinic and aromatic oils, distillation residue alcohol C ₁₀ and mixtures thereof.

6. The composition of Embodiment 5, wherein the composition consists essentially of a crude corn oil containing component and a carrier fluid.

7. The composition of Embodiment 5 further comprising a fatty acid component, wherein the fatty acid component comprises a fatty acid having a C ₈ to C ₁₀ alkyl chain length and no functional groups.

8. The composition of Embodiment 2, wherein the precipitation solution crystallization process is a Bayer process.

9. Composition according to embodiment 1, wherein the composition contains a biodiesel component, wherein the biodiesel contains 90 wt.% or more of methyl esters of C ₁₆ , C ₁₈ or C ₂₂ acids and 0-2 wt.% free fatty acids.

10. The composition of embodiment 9, wherein the composition contains 40-100% by weight of a biodiesel component.

11. The composition of embodiment 9, wherein the composition contains 98-100% by weight of a biodiesel component.

12. The composition of Embodiment 9, comprising a volume of carrier fluid, wherein the hydrocarbon fluid is a hydrocarbon oil containing aliphatic or aromatic oil compounds selected from the group consisting of paraffin oils, naphthenic oils, mixed paraffinic and aromatic oils, distillation residue alcohol C10 and mixtures thereof.

13. The composition of embodiment 12, wherein the composition consists essentially of a biodiesel component and a carrier fluid.

14. The composition of Embodiment 12 further comprising a fatty acid component, wherein the fatty acid component comprises a fatty acid having a C ₈ to C ₁₀ alkyl chain length and no functional groups.

15. The composition of Embodiment 12 wherein the precipitation solution crystallization process is a Bayer process.

16. The composition of Embodiment 9 further comprising a crude corn oil component, wherein the crude corn oil component contains 80% by weight or more of monoalkyl esters, including C ₁₆ and C ₁₈ ethyl esters, diglycerol esters and triglycerol esters of long chain fatty acids; and 0-15 wt.% free fatty acids.

17. The composition of Embodiment 16, wherein the composition consists essentially of a biodiesel component and a crude corn oil component.

18. A method for optimizing the production and extraction of crystalline agglomerates from the precipitation solution of the crystallization process, which includes the following stages:

(i) a step in which a crystal growth modifying composition is added to the precipitation solution in an amount sufficient to increase the particle size of the crystalline agglomerates, containing: 1-100 wt.% of a component containing unrefined corn oil or a biodiesel component, in which, the component , containing unrefined corn oil, contains unrefined corn oil recovered as a separated phase by-product of the ethanol production process; and a biodiesel component containing biodiesel containing methyl esters of long chain fatty acids; and 0-99 wt.% of the carrier fluid, and the carrier fluid contains a hydrocarbon liquid;

(ii) a step in which the crystal growth modifying composition is distributed throughout the precipitation solution; And

(iii) a step in which the crystalline agglomerates are precipitated from the precipitation solution, where the crystal growth modifying composition results in an increase in the particle size of the recovered crystalline agglomerates compared to a crystallization process in the precipitation solution in the absence of a crystal growth modifier.

19. The method of Embodiment 18 wherein the crystal growth modifying composition comprises a crude corn oil containing component, wherein the crude corn oil containing component contains 80% by weight or more of monoalkyl esters, including ethyl esters of _C16 and C ₁₈ esters of diglycerols and triglycerol esters of long chain fatty acids; and 0-15 wt.% free fatty acids.

20. The method of Embodiment 19 wherein the crystal growth modifying composition comprises 98-100% by weight of a crude corn oil containing component.

21. The method of Embodiment 19 wherein the crystal growth modifying composition comprises a volume of carrier fluid wherein the hydrocarbon fluid is a hydrocarbon oil containing aliphatic or aromatic oil compounds selected from the group consisting of paraffin oils, naphthenic oils, mixed paraffinic and aromatic oils, the residue of the distillation of alcohol C ₁₀ and mixtures thereof.

22. The composition of Embodiment 21 wherein the crystal growth modifying composition consists essentially of a crude corn oil containing component and a carrier fluid.

23. The method of Embodiment 18 wherein the crystal growth modifying composition comprises a biodiesel component, wherein the biodiesel component contains 90% by weight or more of C ₁₆ , C ₁₈ or C ₂₂ acid methyl esters and 0-2 wt % free fatty acids. acids.

24. The method of Embodiment 23, wherein the crystal growth modifying composition contains 98-100% by weight of a biodiesel component.

25. The method of Embodiment 23 wherein the crystal growth modifying composition comprises a volume of carrier fluid wherein the hydrocarbon fluid is a hydrocarbon oil containing aliphatic or aromatic oil compounds selected from the group consisting of paraffin oils, naphthenic oils, mixed paraffinic and aromatic oils, the residue of the distillation of Xu alcohol and their mixtures.

26. The composition of Embodiment 25, wherein the crystal growth modifying composition consists essentially of a crude corn oil containing component and a carrier fluid.

27. The method of Embodiment 23 further comprising a crude corn oil containing component, wherein the crude corn oil containing component contains 80% by weight or more of monoalkyl esters, including C ₁₆ and Cis ethyl esters, diglycerol esters, and triglycerol esters of long chain fatty acids; and 0-15 wt.% free fatty acids.

28. The method of Embodiment 27 wherein the crystal growth modifying composition consists essentially of a biodiesel component and a crude corn oil component.

29. The method of Embodiment 18 wherein the crystal growth modifying composition is added to the precipitation solution in one or more of the following Bayer process steps:

(i) to the precipitation solution feed stream;

(ii) into a suspension of embryos;

(iii) into the settling tank; and (iv) into the existing settling tank inlet stream.

30. A method for the production of aluminum hydroxide from a Bayer production solution containing an aqueous phase of sodium aluminate, a solution obtained after separation of caustic-insoluble suspended solids, where the method includes the following steps:

(i) a step in which a crystal growth modifying composition is added to the Bayer process precipitation solution;

(ii) a step in which the crystal growth modifying composition is distributed throughout the precipitation solution; and (iii) a step in which crystalline agglomerates are precipitated from the precipitation solution, wherein the precipitation solution has an upper operating temperature that is not exceeded in steps (i), (ii) and (iii), and the crystal growth modifying composition is selected from the group , consisting of:

(a) the first composition containing 40-100 wt.% component containing unrefined corn oil, and the component containing unrefined corn oil, contains unrefined corn oil, extracted as a by-product of the ethanol production process released into a separate phase, and contains 80 wt. % or more complex monoalkyl esters, including complex ethyl esters of acids C ₁₆ and C ₁₈ esters of diglycerol and triglycerol esters of long chain fatty acids and 0-15 wt.% free fatty acids; and 0-60 wt.% liquid

- 10 040865 sti-carrier, and the carrier fluid is a hydrocarbon liquid having a boiling point above the upper operating temperature, (b) the second composition containing 40-100 wt.% biodiesel component containing biodiesel containing 90 wt.% or more complex methyl esters of acids With ₁₆ With ₁₈ or C22 and 0-2 wt.% free fatty acids; and 0-60 wt.% carrier fluid, and the carrier fluid is a hydrocarbon liquid having a boiling point above the upper operating temperature, and (c) a third composition containing 10-90 wt.% of the first composition and 10-90 wt. % of the second composition, and the composition that modifies the growth of crystals is added in an amount sufficient to shift the particle size distribution for aluminum hydroxide crystals in the direction of reducing the formation of fine particles, and moreover, in cases where the first or third compositions are selected, then ethyl esters, esters of diglycerol and esters of triglycerol, or in cases where the second or third composition is chosen, the methyl esters are hydrolyzed in the precipitation solution to form fatty acids.

31. The method of embodiment 30 wherein the crystal growth modifying composition comprises a volume of carrier fluid wherein the hydrocarbon fluid is a hydrocarbon oil containing aliphatic or aromatic oil compounds selected from the group consisting of paraffin oils, naphthenic oils, mixed paraffinic and aromatic oils, the residue of the distillation of alcohol C ₁₀ and mixtures thereof.

Examples

The foregoing may become clearer with reference to the following examples, which are presented for illustrative purposes and are not intended to limit the scope of the invention. In particular, the examples demonstrate typical examples of the principles embodied in the invention. These principles are not strictly limited to the specific conditions given in these examples. Therefore, it should be understood that the invention covers various changes and modifications of the examples described in this document. Such changes and modifications may be made without departing from the spirit and scope of the invention and without diminishing its intended benefits. Therefore, such changes and modifications are intended to be covered by the appended claims.

For illustrative purposes and without intending to limit the scope of the invention, deposition testing was conducted with CGM compositions (example 1 and example 2) prepared in accordance with some embodiments of the invention. These CGM compositions were compared with other crystal growth modifiers and with controls. The tests were carried out using a fresh mother liquor obtained from the reconstitution of a factory waste liquor.

Deposition Test Method

The tests were carried out using either a fresh mother liquor obtained from an alumina refinery or using a reconstituted mother liquor prepared by adding aluminum hydroxide to the factory spent liquor. Sedimentation tests were carried out on 250 ml Nalgene® bottles, which were rotated from bottom to cap at approximately 10-15 rpm, in an Intronics temperature controlled water bath. Approximately 200 ml of the solution were accurately measured into a row of bottles. Additives, when required, were measured into appropriate bottles, and then all bottles were placed in a spinning bath to equilibrate at a given test temperature (from about 63°C to about 71°C (from about 145°F to about 160 °F)). After bringing to an equilibrium state, the bottles were removed, quickly loaded with a given number of embryos and immediately returned to the water bath. The bottles were rotated for a given test period, typically four to six hours.

After completion of the test, the bottles were removed from the bath. The SC of the remaining suspension was added with 10 ml of sodium gluconate solution (400 g/l) and mixed well to prevent further precipitation. The solids were collected by vacuum filtration, washed thoroughly with hot deionized water and dried at 110°C.

Particle size distribution and specific surface area were determined using a Malvern Particle Sizer. The results are illustrated in the following table. III and IV. The particle size distribution is represented by three quantiles, d(0.1), d(0.5) and d(0.9). They represent the diameters below which 10%, 50% and 90% of particles by volume fall, respectively. The percentage increase over the control quantile particle size is the difference between the added additive and the control sample for the corresponding particle size quantile divided by the particle size of the control quantile. The effect of CGM on particle size distribution is determined by the increase in the percentage of particles larger than 45 µm (commercial aluminum hydroxide size is commonly monitored in the industry) in the precipitation product relative to a control sample without additive. The larger the magnification, the better the CGM performance in terms of producing large crystals.

Test specimens and test specimens

Two samples from Example 1 and two samples from Example 2 were individually compared to two controls (no crystal growth modifiers) and two samples each of commercial products N7837 and N85651 using the precipitation test procedure described above. The test results are described and shown in the following table. III and IV. The tested samples had the following compositions.

The sample labeled Example 1 had a biodiesel formula according to an embodiment of the invention containing 20% biodiesel and 80% hydrocarbon oil, where the biodiesel was a methyl ester from soybean oil.

The sample labeled Example 2 had a crude corn oil formula according to an embodiment of the invention containing 40% crude corn oil derived from a bioethanol process and 60% hydrocarbon oil.

Sample designations N7837 and N85651 are commercial crystal growth modifiers available from Nalco Company, Naperville, Ill. called Nalco Product Nos. 7837 and 85651, respectively.

In table. III and IV show the effect of examples 1 and 2 on the particle size of aluminum hydroxide produced in the Bayer process and comparing the values of examples 1 and 2, respectively, with the results for the control sample (without CGM) and production samples N7837 and N85651, as described above . The data given for the +45.7 µm % fraction is the average of three identical samples. The samples were tested using a double run with the same dose of 3 mg/m ² of the surface of the embryos (60 ppm compared to the aluminate solution); equal numbers of embryos were loaded into sample bottles; and the bottles were rotated with the same exposure periods (test duration).

Example 1 Test and results.

When testing the sample of example 1, the solution was a fresh mother liquor with A/C=0.65; and the test temperature (deposition temperature) during the holding period was 70°C.

The comparison results are given in table. III.

Table III

SAMPLES doses A, h/m ln. PARTICLE SIZE QUANTILES % INCREASE AVERAGE PARTICLE SIZE VALUES OF CONTROL QUANTILES D(0,l) , µm D(0.5) , µm D(0.9) , µm +45.7 µm, % D(0,l) , µm D(0.5) , µm D(0.9) , µm +45.7 µm, % Control 1 - 28.54 50.25 85.89 59.71 Control 2 - 28.86 50.26 85.02 59.90 Average 28.70 50.26 85.46 59.80 N7837 60 31.34 54.34 91.38 68.66 N7837 60 30.93 53.66 90.11 69.08 Average 31.13 54.00 90.75 68.87 08% 07% 06% 15% N85651 60 30.98 53.61 89.94 65.59 N85651 60 29.92 52.20 88.42 63.13 Average 30.45 52.91 89.18 64.36 06% 05% 04% 08% Example 1 60 31.20 54.34 91.71 66.55 Example 1 60 30.44 52.94 88.97 66.44 Average 30.82 53.64 90.34 65.49 07% 07% 06% eleven%

The results are given in table. III, show that the sample of example 1, having the formula of biodiesel in accordance with the present invention, provides a % fraction of +45 μm compared to the control sample without additive. In addition, the table shows that the sample with the biodiesel formula is superior to the commercial crystal growth modifier N85651. Surprisingly, the biodiesel-formulated sample, despite using more biodiesel than traditional active ingredients, resulted in an increase in CGM activity to a level comparable to commercial CGM activity.

Example 2 Test and results.

When testing the sample of example 2, the solution was a fresh mother liquor with A/C=0.70; and the test temperature (deposition temperature) during the holding period was 70°C. The comparison results are given in table. IV.

- 12 040865

Table IV

SAMPLES DOSE ppm PARTICLE SIZE QUANTILE % INCREASE IN THE MEAN PARTICLE SIZE OF THE CONTROL QUANTILE D(0,l) , µm D(0.5) , µm D(0.9) , µm +45.7 µm, % D(0,l) , µm D(0.5) , µm D(0.9) , µm +45.7 µm, % Control 1 - 31.74 60.35 103.11 71.42 Control 2 - 31.52 57.00 100.51 69.17 Average 31.63 58.67 101.81 70.30 N7837 60 36.58 62.84 106.14 78.05 N7837 60 38.40 63.09 101.84 80.51 Average 37.49 62.96 103.99 79.28 19% 07% 02% 13% N85651 60 34.42 59.83 101.67 74.10 N85651 60 35.09 60.81 103.09 75.41 Average 34.75 60.32 102.38 74.75 10% 03% 01% 06% Example 2 60 37.35 64.70 109.37 79.75 Example 2 60 38.36 65.70 109.68 81.26 Average 37.85 65.20 109.53 80.51 20% eleven% 08% 15%

The results are given in table. IV, show that the sample of example 2, having a crude corn oil formula according to the present invention, provides a % fraction of +45 μm compared to the control sample without additive. In addition, the table shows that the unrefined corn oil formula sample outperformed both commercial crystal growth modifiers, N7837 and N85651. Surprisingly, the raw corn oil formula sample, despite using unrefined corn oil extracted from the bioethanol process to a greater extent than conventional active ingredients, resulted in an increase in CGM activity to a level superior to commercial CGM.

While this invention may be embodied in many different forms, particular embodiments are described in detail herein. The present disclosure is illustrative examples of the principles of the invention, and is not intended to limit the invention to the illustrated particular variants of its implementation. In addition, the invention covers any possible combinations of some or all of the various implementation options described in this document and/or introduced into it. Additionally, the invention covers any possible combinations that also specifically exclude any one or some of the various implementation options mentioned in this document, described in this document and/or entered into it.

The invention is not limited to the details of the embodiment(s) described above. The invention extends to any new variation or any new combination of features described in this specification (including any reference by reference, any accompanying claims and abstract), or to any new step or to any new combination of steps of any of the disclosed methods or processes.

Those of ordinary skill in the relevant arts will appreciate that various embodiments of the invention may include fewer features than are illustrated in any of the individual embodiments described above. The implementations described herein should not be taken as an exhaustive presentation of the ways in which the various features can be combined. Accordingly, the implementations are not mutually exclusive combinations of features; rather, the claims may include various individual features selected from various individual embodiments, as will be understood by those of ordinary skill in the art.

All ranges and parameters disclosed herein are to be understood as covering any and all subranges included therein and every number between the endpoints. For example, a stated range of 1 to 10 should be considered to include any and all sub-ranges of (and including) a minimum value of 1 and a maximum value of 10; this means that all sub-ranges are covered, ranging from a minimum value of 1 or more, (for example, from 1 to 6.1), and ending

-

Claims (13)

a maximum value of 10 or less (for example, 2.3 to 9.4, 3 to 8, 4 to 7), and finally each number 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 contained within the range. All percentages, ratios, and fractions in this document are by weight unless otherwise noted. References to embodiment(s), the disclosure, this disclosure, embodiment(s) of the disclosure, disclosed/disclosed embodiment(s), etc. contained in this document refer to the specification (text including claims, and figure) of this patent application, which is not considered state of the art. For the purposes of interpreting the claims, it is expressly contemplated that the provisions of 35 USC § 112(f) need not be invoked except where the specific term is intended to or step is used in the relevant claim. This completes the description of the various embodiments of the invention. Those skilled in the art may find other equivalents to the specific embodiments described herein, and it is intended that these equivalents be covered by the claims appended to this document. CLAIM 1. Composition for optimizing the production of crystalline aluminum hydroxide agglomerates from the precipitation solution during crystallization, containing: (a) a precipitation solution containing aluminate; and (b) 0.01-400 mg per liter of the precipitation solution of the crystal growth modifier composition, wherein the crystal growth modifier composition contains 1-100 wt.% of a component containing unrefined corn oil, or a mixture containing a component with unrefined corn oil and a component with biodiesel, wherein the crude corn oil component contains crude corn oil, which is extracted as a by-product in the bioethanol process, and includes monoalkyl esters, diglyceride esters, and triglyceride esters of long chain fatty acids, and the biodiesel component in said mixture contains methyl esters of long chain fatty acids, and moreover, the balance of the composition of the crystal growth modifier is a carrier liquid containing a hydrocarbon liquid. 2. The composition of claim 1, wherein the crude corn oil component contains 80 wt% or more of monoalkyl esters, including C ₁₆ and C ₁₈ ethyl esters, diglyceride esters, and long chain fatty acid triglyceride esters. 3. The composition according to claim 1 or 2, characterized in that the composition of the crystal growth modifier contains 98-100 wt.% component containing unrefined corn oil. 4. The composition according to any one of claims 1 to 3, characterized in that the composition of the crystal growth modifier consists of unrefined corn oil and a carrier liquid, and the hydrocarbon liquid is a hydrocarbon oil containing aliphatic or aromatic oil compounds selected from the group consisting of from paraffinic oils, naphthenic oils, mixed paraffinic and aromatic oils, the distillation residue of C ₁₀ alcohol and mixtures thereof. 5. Composition according to claim 1, characterized in that the composition of the crystal growth modifier contains a component with biodiesel, and biodiesel contains 90 wt.% or more C ₁₆ , C ₁₈ or C ₂₂ methyl esters. 6. Composition according to any one of claims 1-2, 5, characterized in that the composition of the crystal growth modifier contains a component with crude corn oil and a component with biodiesel, and the component with crude corn oil contains 80 wt.% or more complex monoalkyl esters, including C16 and C ₁₈ ethyl esters, diglyceride esters and triglyceride esters of long chain fatty acids, and biodiesel contains 90 wt.% or more C ₁₆ , C ₁₈ or C ₂₂ methyl esters. 7. Composition according to claim 6, characterized in that the composition of the crystal growth modifier consists of a mixture of a component with biodiesel and a component with unrefined corn oil. 8. The composition according to claim 6, characterized in that the composition of the crystal growth modifier consists of a component with biodiesel and a component with unrefined corn oil and a carrier liquid, and the hydrocarbon liquid is a hydrocarbon oil containing aliphatic or aromatic oil compounds selected from the group consisting of from paraffinic oils, naphthenic oils, mixed paraffinic and aromatic oils, the distillation residue of C ₁₀ alcohol and mixtures thereof. 9. The composition according to claim 1, characterized in that the composition of the crystal growth modifier contains 40-100 wt.% component containing crude corn oil, or a mixture of crude corn oil and biodiesel, which contains 10-90 wt.% crude corn oil and 10-90 wt.% biodiesel, so that when the amount of the composition is added to the precipitation - 14 040865 solution of the crystallization process, ethyl esters, diglyceride esters, triglyceride esters and methyl esters of crude corn oil, biodiesel or a mixture of crude corn oil and biodiesel are hydrolyzed in the precipitation solution to form fatty acids. 10. A method for optimizing the production and recovery of crystalline aluminum hydroxide agglomerates from the precipitation solution during crystallization, comprising the following steps: (i) a step in which a crystal growth modifier composition is added to the precipitation solution in an amount of 0.01 to 400 mg per liter of the precipitation solution, wherein the crystal growth modifier composition contains 1-100 wt.% of a component containing unrefined corn oil, or a blend containing a crude corn oil component and a biodiesel component, wherein the corn oil is extracted as a by-product in the bioethanol process, and contains 80 wt% or more of monoalkyl esters, including ethyl esters of Cie and Cis acids, diglyceride esters, and triglyceride esters of long chain fatty acids, and wherein the biodiesel component contains methyl esters of long chain fatty acids and contains 90 wt.% or more of Cu, Ci ₈ or C ₂₂ methyl esters, and wherein the balance of the composition of the crystal growth modifier is a carrier liquid containing hydrocarbon liquid, and; (ii) a step in which the composition of the crystal growth modifier is distributed over the precipitation solution; and (iii) a step in which the crystalline agglomerates are precipitated from the precipitation solution. 11. The method according to claim 10, characterized in that the crystal growth modifier composition contains 98-100 wt.% of a component containing unrefined corn oil or a mixture of a component with unrefined corn oil and a biodiesel component. 12. The method according to claim 10 or 11, characterized in that the composition of the crystal growth modifier consists of a crude corn oil component, or a mixture of a crude corn oil component and a biodiesel component, and a carrier fluid represented by a hydrocarbon liquid, wherein the hydrocarbon liquid is a hydrocarbon oil containing aliphatic or aromatic oil compounds selected from the group consisting of paraffin oils, naphthenic oils, mixed paraffinic and aromatic oils, a distillation residue of Xiu alcohol, and mixtures thereof. 13. The method according to claim 10, characterized in that the composition of the crystal growth modifier contains 40-100 wt.% component with unrefined corn oil, or a mixture of a component with unrefined corn oil and a component with biodiesel, and a mixture containing a component with unrefined corn oil and the biodiesel component contains 10-90 wt.% crude corn oil and 10-90 wt.% biodiesel. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2