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WO2007109328A2 - Glycerin by-procucts and methods of using same - Google Patents

Glycerin by-procucts and methods of using same Download PDF

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Publication number
WO2007109328A2
WO2007109328A2 PCT/US2007/007033 US2007007033W WO2007109328A2 WO 2007109328 A2 WO2007109328 A2 WO 2007109328A2 US 2007007033 W US2007007033 W US 2007007033W WO 2007109328 A2 WO2007109328 A2 WO 2007109328A2
Authority
WO
WIPO (PCT)
Prior art keywords
grinding
glycerin
product
grinding aid
weight percent
Prior art date
Application number
PCT/US2007/007033
Other languages
French (fr)
Other versions
WO2007109328A3 (en
Inventor
Bo L. Tran
Sankar Bhattacharja
Original Assignee
Nalco Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nalco Company filed Critical Nalco Company
Priority to MX2008012079A priority Critical patent/MX2008012079A/en
Priority to BRPI0709339-0A priority patent/BRPI0709339A2/en
Priority to CA2677340A priority patent/CA2677340C/en
Publication of WO2007109328A2 publication Critical patent/WO2007109328A2/en
Publication of WO2007109328A3 publication Critical patent/WO2007109328A3/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/06—Selection or use of additives to aid disintegrating
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/001—Waste organic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/02—Alcohols; Phenols; Ethers
    • C04B24/023—Ethers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/48—Clinker treatment
    • C04B7/52—Grinding ; After-treatment of ground cement
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/52—Grinding aids; Additives added during grinding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the present invention relates generally to grinding aid technologies. More specifically, the present invention relates to grinding aid compositions and methods of using the same.
  • the grinding operation consumes substantial quantities of energy. As the particles get finer, grinding progressively becomes more energy intensive. It is, therefore, a common practice to employ grinding aids which increase the efficiency of the grinding operation and thereby the throughput of the grinding mill.
  • Grinding aids are materials that facilitate grinding in ball, rod, or roller mills by compensating the charges on freshly broken surfaces. Through adsorption of the molecules of grinding aids to the surfaces of ground particles, the surface energy requirements are satisfied. This minimizes particle agglomeration and prevents caking of the mill interior wall and coating of the grinding media. Mill efficiency and throughput are increased as a result.
  • grinding aid formulations are based on glycols. It is desirable to provide and utilize cost-effective grinding aids that are environmentally friendly and preferably derived from renewable sources.
  • the present invention relates generally to grinding aid technologies. More specifically, the present invention relates to grinding aid compositions and methods of using the same.
  • the present invention provides a method of efficiently grinding solid materials.
  • the method can comprise mixing the solid material with the grinding aid, and using a grinding media such as steel balls to grind the solids. Grinding aid can also be introduced during the grinding operation.
  • the grinding aid composition can comprise one or more glycerin by-products derived from a biodiesel manufacturing process.
  • the grinding aid composition can also comprise one or more glycerin by-products of transesterification reactions involving triglycerides.
  • the grinding aid can be added to the grinding process as a solution.
  • the glycerin by-product can be generated during the manufacture of biodiesel.
  • Biodiesel can be manufactured through a transesterif ⁇ cation process in which vegetable oils and/or animal fats are converted to fatty acid alkyl esters and by-products containing glycerin.
  • the glycerin by-product comprises about 50 to about 95 weight percent of glycerin.
  • the glycerin by-product further comprises one or more components selected from the group consisting of methyl esters, non-glycerol organic material, collectively called "MONG", salts, methanol, water and combinations thereof.
  • MONG methyl esters, non-glycerol organic material
  • the glycerin by-product further comprises one or more inorganic salts.
  • the present invention provides a method of efficiently grinding solid material.
  • the method can comprise adding a grinding aid composition to the solid material to reduce the energy requirement to grind the solid material.
  • the grinding aid composition can comprise one or more glycerin byproducts derived from a biodiesel manufacturing process. Grinding aid facilitates grinding in ball, rod, or roller mills, by eliminating ball coating and caking by dispersing the ground solid material.
  • the grinding aid can be added in solution to the mill feed or directly into the mill itself. The grinding aid prevents ball coating and consequently mill efficiency is increased. Power cost is thus reduced.
  • the present invention provides a grinding aid composition comprising glycerin by-products of transesterification reactions involving triglycerides.
  • An advantage of the present invention is to provide cost-effective method of grinding solid materials.
  • the present invention offers further advantages in that it is environmentally friendly and derived from renewable sources.
  • the present invention relates generally to grinding aid technologies. More specifically, the present invention relates to grinding aid compositions comprising glycerin containing by-products of biodiesel manufacturing processes, and/or transesterification reactions involving triglycerides and methods of using same.
  • grinding aid should be understood to mean compositions that facilitate grinding. Suitable processes for accomplishing this include, but are not limited to, grinding portland cement clinker, calcined and non- calcined limestone, and similar technologies.
  • by-products should be understood to mean by-products derived from biodiesel manufacturing processes, and/or transesterification reactions involving triglycerides.
  • Environmentally friendly means non-hazardous, non-toxic, biodegradable, and derived from renewable sources.
  • the present invention provides grinding aid compositions comprising glycerin-containing by-products of transesterification reactions involving triglycerides.
  • the present invention provides grinding aid compositions comprising glycerin-containing by-products of biodiesel manufacturing processes.
  • the glycerin by-products of biodiesel manufacturing of the present invention can be economic and- effective grinding aids, for example, to grind portland cement clinker.
  • the glycerin by-products are environmentally friendly and derived from renewable sources.
  • the glycerin by-products are also non-flammable and can provide benefits in applications where there is a "high or no" flash point requirement.
  • portland cement clinker is often ground when it is hotter than 50 0 C.
  • the glycerin by-products can be used to supplement or replace conventional hazardous grinding aids such as glycol mixtures that include ethylene glycol, a toxic material.
  • Biodiesel is a cleaner-burning diesel replacement fuel made from natural, renewable sources.
  • biodiesel can include fatty acid alkyl esters used as a cleaner-burning diesel replacement fuel made from sources such as new and used vegetable oils and animal fats.
  • Biodiesel can be made through a chemical process called transesterification in which vegetable oil or animal fats are converted to fatty acid alkyl esters and glycerin by-products.
  • oils and fats include, for example, tallow, crude tall oil, coconut oil, rapeseed oil, canola oil, palm kernel oil and soybean, oil.
  • Triglycerides the principal components of animal fats and of vegetable oils, are esters of glycerol, a trihydric alcohol, with fatty acids of varying molecular weight.
  • fatty acid alkyl esters from oils and fats: base-catalyzed transesterification of the oil; direct acid-catalyzed esterification of the oil; and conversion of the oil to fatty acids and subsequent esterification to biodiesel.
  • the majority of fatty acid alkyl esters are produced by the base-catalyzed method.
  • the catalyst used for transesterification of the oil to produce biodiesel commercially can be typically any base, most preferably sodium hydroxide or potassium hydroxide.
  • the oils and fats can be filtered and preprocessed to remove water and contaminants. If free fatty acids are present, they can be removed or transformed into biodiesel using special pretreatment technologies, such as acid catalyzed esterification.
  • the pretreated oils and fats can then be mixed with an alcohol and a catalyst (e.g. base).
  • the base used for the reaction is typically sodium hydroxide or potassium hydroxide, being dissolved in the alcohol used (typically ethanol or methanol) to form the corresponding alkoxide, with standard agitation or mixing. It should be appreciated that any suitable base can be used.
  • the alkoxide may then be charged into a closed reaction vessel, and the oils and fats are added.
  • the system can then be closed, and held at about 71 0 C (160 0 F) for a period of about I to 8 hours, although some systems recommend that the reactions take place at room temperature.
  • oil molecules e.g. triglycerides
  • two major products are produced: 1) a crude fatty acid alkyl esters phase (i.e. biodiesel phase) and 2) a glycerin by-product phase.
  • the crude fatty acid alkyl esters phase forms a layer on top of the denser glycerin by-product phase.
  • the glycerin by-product phase is denser than the biodiesel phase, the two can be gravity separated.
  • the glycerin by-product phase can be simply drawn off the bottom of a settling vessel. In some cases, a centrifuge may be employed to speed the separation of the two phases.
  • the glycerin by-product phase typically consists of a mixture of glycerin, methyl esters, methanol, mong, inorganic salts and water.
  • Mong is "matiere organique non glycerol”.
  • Mong normally consists of soaps, free fatty acids, and other impurities.
  • Typical inorganic salts include, for example, salts (e.g. chlorides and sulfates) of sodium, potassium and/or calcium.
  • the by-products can contain about 0.1 to about 7 weight percent of the inorganic salts.
  • the inorganic salts are selected from sodium and potassium chloride.
  • the glycerin by-product phase comprises a mixture of about 50 to about 95 weight percent glycerin, about 0.01 to about 5 weight percent methyl esters and methanol, about 0.1 to about 3 weight percent mong, about 0.1 to about 7 weight percent inorganic salts and about 4 to about 49 weight percent water.
  • the glycerin by-products of biodiesel manufacturing are inexpensive and their use can be economical and effective for a variety of grinding aid technologies.
  • this invention offers an alternative to existing grinding aid formulations such as those disclosed in Patent No. 4,204,877 which describes the use of di-, tri-, and tctraglyccrol, and mixtures thereof.
  • the present invention offers an alternative that is economical and derived from renewable sources.
  • the present invention provides methods of grinding solid materials.
  • the grinding aid compositions comprising the glycerin byproducts can be useful in grinding the following materials including, but not limited to, Portland cement clinker, calcined and non-calcined limestone, mineral ores, oxide and non-oxide ceramics, or man-made matter.
  • the grinding aid compositions can also be used in conjunction with other suitable grinding aid formulations and/or cement or concrete additives. These additives can be mixed with the byproduct glycerin grinding aid and used to control setting behavior of portland cement and prevent deleterious reactions in concrete that compromise durability.
  • the solid is portland cement clinker.
  • the portland cement clinker is formed by pyroprocessing an intimate mixture of finely ground limestone, clay, and suitable source of iron oxide.
  • the clinker is ground with the addition of about 3 to about 5 percent of gypsum to control the setting properties of the finished cement. Small amounts of other substances may be added during grinding to impart special properties to the product.
  • Portland cement is commonly ground to 90% (by mass) finer than 44 ⁇ m (325-mesh).
  • Grinding aids are materials that facilitate grinding by eliminating caking and ball coating by dispersing the material being ground.
  • the grinding aids may be added in concentrated form or may be diluted with up to about 50 weight percent of water or other suitable diluents, or a mixture thereof.
  • the grinding aids may be added to the mill feed or directly into the mill itself.
  • Grinding aids used in grinding cement clinker are added from 0.006% to 0.08% of the clinker weight.
  • the majority of grinding aids are substances work by adsorption to the ground particles, so that surface charge requirements are satisfied, which reduces the number of unsatisfied bonds to attract other particles and cause agglomeration. Grinding aids improves mill efficiency by increasing throughput, reducing power demand, and smoothing operations.
  • Grinding aids also increase the efficiency of air separators by dispersing the solids so that the smaller solids are not carried by the larger ones. This improves the classification process and assist meeting the quality requirements. By elimination of the surface energy forces that normally cause inter-particle attraction, grinding aids improve flowability after grinding and prevents hang-ups in storage silos.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Disintegrating Or Milling (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

Methods and compositions for grinding materials are provided. In an embodiment, the present invention provides a method of grinding solid materials. For example, the method can comprise mixing the solid material with the grinding aid, and using a grinding media such as steel balls to grind the solids. The grinding aid composition can comprise one or more glycerin by-products derived from a biodiesel manufacturing process. The grinding aid composition can also comprise one or more glycerin by-products of transesterification reactions involving triglycerides. The grinding aid can be added to the grinding process as a solution.

Description

GLYCERIN BY-PRODUCTS AND METHODS OF USING SAME
BACKGROUND
The present invention relates generally to grinding aid technologies. More specifically, the present invention relates to grinding aid compositions and methods of using the same.
The grinding operation consumes substantial quantities of energy. As the particles get finer, grinding progressively becomes more energy intensive. It is, therefore, a common practice to employ grinding aids which increase the efficiency of the grinding operation and thereby the throughput of the grinding mill.
Grinding aids are materials that facilitate grinding in ball, rod, or roller mills by compensating the charges on freshly broken surfaces. Through adsorption of the molecules of grinding aids to the surfaces of ground particles, the surface energy requirements are satisfied. This minimizes particle agglomeration and prevents caking of the mill interior wall and coating of the grinding media. Mill efficiency and throughput are increased as a result.
Many grinding aid formulations are based on glycols. It is desirable to provide and utilize cost-effective grinding aids that are environmentally friendly and preferably derived from renewable sources.
SUMMARY
The present invention relates generally to grinding aid technologies. More specifically, the present invention relates to grinding aid compositions and methods of using the same. In an embodiment, the present invention provides a method of efficiently grinding solid materials. For example, the method can comprise mixing the solid material with the grinding aid, and using a grinding media such as steel balls to grind the solids. Grinding aid can also be introduced during the grinding operation. The grinding aid composition can comprise one or more glycerin by-products derived from a biodiesel manufacturing process. The grinding aid composition can also comprise one or more glycerin by-products of transesterification reactions involving triglycerides. The grinding aid can be added to the grinding process as a solution. In an embodiment, the glycerin by-product can be generated during the manufacture of biodiesel. Biodiesel can be manufactured through a transesterifϊcation process in which vegetable oils and/or animal fats are converted to fatty acid alkyl esters and by-products containing glycerin. In an embodiment, the glycerin by-product comprises about 50 to about 95 weight percent of glycerin.
In an embodiment, the glycerin by-product further comprises one or more components selected from the group consisting of methyl esters, non-glycerol organic material, collectively called "MONG", salts, methanol, water and combinations thereof.
In an embodiment, the glycerin by-product further comprises one or more inorganic salts.
In another embodiment, the present invention provides a method of efficiently grinding solid material. For example, the method can comprise adding a grinding aid composition to the solid material to reduce the energy requirement to grind the solid material. The grinding aid composition can comprise one or more glycerin byproducts derived from a biodiesel manufacturing process. Grinding aid facilitates grinding in ball, rod, or roller mills, by eliminating ball coating and caking by dispersing the ground solid material. The grinding aid can be added in solution to the mill feed or directly into the mill itself. The grinding aid prevents ball coating and consequently mill efficiency is increased. Power cost is thus reduced.
In another embodiment, the present invention provides a grinding aid composition comprising glycerin by-products of transesterification reactions involving triglycerides. An advantage of the present invention is to provide cost-effective method of grinding solid materials. The present invention offers further advantages in that it is environmentally friendly and derived from renewable sources.
Additional features and advantages are described herein, and will be apparent from, the following Detailed Description. DETAILED DESCRIPTION
The present invention relates generally to grinding aid technologies. More specifically, the present invention relates to grinding aid compositions comprising glycerin containing by-products of biodiesel manufacturing processes, and/or transesterification reactions involving triglycerides and methods of using same.
In -the present specification, the term "grinding aid" should be understood to mean compositions that facilitate grinding. Suitable processes for accomplishing this include, but are not limited to, grinding portland cement clinker, calcined and non- calcined limestone, and similar technologies. In the present specification, the term "by-products" should be understood to mean by-products derived from biodiesel manufacturing processes, and/or transesterification reactions involving triglycerides. Environmentally friendly means non-hazardous, non-toxic, biodegradable, and derived from renewable sources.
In an embodiment, the present invention provides grinding aid compositions comprising glycerin-containing by-products of transesterification reactions involving triglycerides.
In an embodiment, the present invention provides grinding aid compositions comprising glycerin-containing by-products of biodiesel manufacturing processes.
The glycerin by-products of biodiesel manufacturing of the present invention can be economic and- effective grinding aids, for example, to grind portland cement clinker. In addition, the glycerin by-products are environmentally friendly and derived from renewable sources. The glycerin by-products are also non-flammable and can provide benefits in applications where there is a "high or no" flash point requirement. For example, portland cement clinker is often ground when it is hotter than 500C. The glycerin by-products can be used to supplement or replace conventional hazardous grinding aids such as glycol mixtures that include ethylene glycol, a toxic material. The present invention offers an added benefit of not posing any environmental and/or human health hazard if accidentally released into the environment and/or if contacted by humans and/or animals. Biodiesel is a cleaner-burning diesel replacement fuel made from natural, renewable sources. For example, biodiesel can include fatty acid alkyl esters used as a cleaner-burning diesel replacement fuel made from sources such as new and used vegetable oils and animal fats.
According to the American Fuel Data Center of the U.S. Department of Energy, approximately 55% of the biodiesel is currently produced from recycled fat or oil feedstock, including recycled cooking grease. The other half of the industry is limited to vegetable oils, the least expensive of which is soy oil. The soy industry has been the driving force behind biodiesel commercialization because of excess production capacity, product surpluses, and declining prices. Similar issues apply to the recycled grease and animal fats industry, even though these feedstocks are less expensive than soy oils. Based on the combined resources of both industries, there is enough of the feedstock to supply 1.9 billion gallons of biodiesel.
Biodiesel can be made through a chemical process called transesterification in which vegetable oil or animal fats are converted to fatty acid alkyl esters and glycerin by-products. Such oils and fats include, for example, tallow, crude tall oil, coconut oil, rapeseed oil, canola oil, palm kernel oil and soybean, oil. Triglycerides, the principal components of animal fats and of vegetable oils, are esters of glycerol, a trihydric alcohol, with fatty acids of varying molecular weight. Three synthetic pathways can be used to produce fatty acid alkyl esters from oils and fats: base-catalyzed transesterification of the oil; direct acid-catalyzed esterification of the oil; and conversion of the oil to fatty acids and subsequent esterification to biodiesel. The majority of fatty acid alkyl esters are produced by the base-catalyzed method. In general, the catalyst used for transesterification of the oil to produce biodiesel commercially can be typically any base, most preferably sodium hydroxide or potassium hydroxide.
In the biodiesel manufacturing process, the oils and fats can be filtered and preprocessed to remove water and contaminants. If free fatty acids are present, they can be removed or transformed into biodiesel using special pretreatment technologies, such as acid catalyzed esterification. The pretreated oils and fats can then be mixed with an alcohol and a catalyst (e.g. base). The base used for the reaction is typically sodium hydroxide or potassium hydroxide, being dissolved in the alcohol used (typically ethanol or methanol) to form the corresponding alkoxide, with standard agitation or mixing. It should be appreciated that any suitable base can be used. The alkoxide may then be charged into a closed reaction vessel, and the oils and fats are added. The system can then be closed, and held at about 710C (1600F) for a period of about I to 8 hours, although some systems recommend that the reactions take place at room temperature.
Once the reactions are complete the oil molecules (e.g. triglycerides) are broken apart and two major products are produced: 1) a crude fatty acid alkyl esters phase (i.e. biodiesel phase) and 2) a glycerin by-product phase. Typically, the crude fatty acid alkyl esters phase forms a layer on top of the denser glycerin by-product phase. Because the glycerin by-product phase is denser than the biodiesel phase, the two can be gravity separated. For example, the glycerin by-product phase can be simply drawn off the bottom of a settling vessel. In some cases, a centrifuge may be employed to speed the separation of the two phases. The glycerin by-product phase typically consists of a mixture of glycerin, methyl esters, methanol, mong, inorganic salts and water. Mong is "matiere organique non glycerol". Mong normally consists of soaps, free fatty acids, and other impurities.
Typical inorganic salts include, for example, salts (e.g. chlorides and sulfates) of sodium, potassium and/or calcium. In an embodiment, the by-products can contain about 0.1 to about 7 weight percent of the inorganic salts. In an embodiment, the inorganic salts are selected from sodium and potassium chloride.
In an embodiment, the glycerin by-product phase comprises a mixture of about 50 to about 95 weight percent glycerin, about 0.01 to about 5 weight percent methyl esters and methanol, about 0.1 to about 3 weight percent mong, about 0.1 to about 7 weight percent inorganic salts and about 4 to about 49 weight percent water.
The glycerin by-products of biodiesel manufacturing are inexpensive and their use can be economical and effective for a variety of grinding aid technologies. For example, this invention offers an alternative to existing grinding aid formulations such as those disclosed in Patent No. 4,204,877 which describes the use of di-, tri-, and tctraglyccrol, and mixtures thereof. The present invention offers an alternative that is economical and derived from renewable sources. In an embodiment, the present invention provides methods of grinding solid materials. For example, the grinding aid compositions comprising the glycerin byproducts can be useful in grinding the following materials including, but not limited to, Portland cement clinker, calcined and non-calcined limestone, mineral ores, oxide and non-oxide ceramics, or man-made matter. The grinding aid compositions can also be used in conjunction with other suitable grinding aid formulations and/or cement or concrete additives. These additives can be mixed with the byproduct glycerin grinding aid and used to control setting behavior of portland cement and prevent deleterious reactions in concrete that compromise durability. In an embodiment, the solid is portland cement clinker.
Tn an embodiment, the portland cement clinker is formed by pyroprocessing an intimate mixture of finely ground limestone, clay, and suitable source of iron oxide. In the case of portland cement, the clinker is ground with the addition of about 3 to about 5 percent of gypsum to control the setting properties of the finished cement. Small amounts of other substances may be added during grinding to impart special properties to the product. Portland cement is commonly ground to 90% (by mass) finer than 44μm (325-mesh).
Grinding aids are materials that facilitate grinding by eliminating caking and ball coating by dispersing the material being ground. The grinding aids may be added in concentrated form or may be diluted with up to about 50 weight percent of water or other suitable diluents, or a mixture thereof. The grinding aids may be added to the mill feed or directly into the mill itself. Grinding aids used in grinding cement clinker are added from 0.006% to 0.08% of the clinker weight. The majority of grinding aids are substances work by adsorption to the ground particles, so that surface charge requirements are satisfied, which reduces the number of unsatisfied bonds to attract other particles and cause agglomeration. Grinding aids improves mill efficiency by increasing throughput, reducing power demand, and smoothing operations. Grinding aids, also increase the efficiency of air separators by dispersing the solids so that the smaller solids are not carried by the larger ones. This improves the classification process and assist meeting the quality requirements. By elimination of the surface energy forces that normally cause inter-particle attraction, grinding aids improve flowability after grinding and prevents hang-ups in storage silos.
[0034] While the present invention is described above in connection with representative or illustrative embodiments, these embodiments are not intended to be exhaustive or limiting of the invention. Rather, the invention is intended to cover all alternatives, modifications and equivalents included within its spirit and scope, as defined by the appended claims.

Claims

1. A method of grinding solids comprising grinding the solids in the presence of a grinding aid composition, wherein the grinding aid composition is a glycerin-containing by-product from a biodiesel manufacturing process or transesterifϊcation reactions involving triglycerides or a mixture thereof.
2. The method of claim 1 wherein the by-product comprises about 50 to about 95 weight percent of glycerin.
3. The method of Claim 2, wherein the by-product is derived from a biodiesel manufacturing process.
4. The method of Claim 2 wherein the by-product is derived from transesterification reactions involving triglycerides.
5. The method of Claim 3, wherein the by-product further comprises one or more components selected from the group consisting of mong, methyl esters, methanol, inorganic salts and water.
6. The method of Claim 5 wherein the by-product comprises about 0.01 to about 7 weight percent of one or more inorganic salts.
7. The method of claim 1 wherein the by-product is be diluted with up to about 50 weight percent of water.
8. The method of claim 1 wherein the grinding is performed in the presence of a grinding media.
9. The method of claim 1 wherein the grinding is performed in a ball, rod, or roller mill.
10. The method of claim 1 wherein the solid is portland cement clinker.
11. A grinding aid composition comprising at least one glycerin-containing by-product derived from a biodiesel manufacturing process or at least one glycerin- containing by-product of transesterifϊcation reactions involving triglycerides or a mixture thereof.
12. The grinding aid composition of claim 1 1 which comprises about 50 to about 90 weight percent of glycerin.
13. The grinding aid composition of claim 12 comprising at least one glycerin-containing by-product of transesterification reactions involving triglycerides.
14. The grinding aid composition of claim 12 comprising at least one glycerin-containing by-product from a biodiesel manufacturing process.
15. The grinding aid composition according to claim 14 wherein the byproduct comprises glycerin, mong, methyl esters, methanol, inorganic salts and water.
16. The grinding agent according to claim 15 wherein the by-product comprises about 0.1 to about 7 weight percent of one or more inorganic salts.
17. The grinding agent composition of claim 11 diluted with up to about 50 weight percent of water.
18. The grinding agent composition of claim 1 1 further comprising grinding media.
PCT/US2007/007033 2006-03-21 2007-03-21 Glycerin by-procucts and methods of using same WO2007109328A2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
MX2008012079A MX2008012079A (en) 2006-03-21 2007-03-21 Glycerin by-procucts and methods of using same.
BRPI0709339-0A BRPI0709339A2 (en) 2006-03-21 2007-03-21 solids grinding method and grinding aid composition
CA2677340A CA2677340C (en) 2006-03-21 2007-03-21 Glycerin by-products and methods of using same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/385,082 2006-03-21
US11/385,082 US7892353B2 (en) 2006-03-21 2006-03-21 Glycerin by-products and methods of using same

Publications (2)

Publication Number Publication Date
WO2007109328A2 true WO2007109328A2 (en) 2007-09-27
WO2007109328A3 WO2007109328A3 (en) 2008-01-03

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FR2953426A1 (en) * 2009-12-07 2011-06-10 Coatex Sas USE OF FORMULATIONS CONTAINING GLYCEROL AS A DRY GRINDING AGENT FOR MINERAL MATERIALS.
WO2011077232A1 (en) 2009-12-24 2011-06-30 Coatex Sas Use of glycerol as an agent to improve the self-dispersing properties of a mineral material to be added to an aqueous composition
US8567703B2 (en) 2008-07-18 2013-10-29 Kao Corporation Method for producing hydraulic powder
EP2692241A1 (en) * 2012-08-02 2014-02-05 Sika Technology AG Food grade grinding aid composition
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WO2011070416A1 (en) 2009-12-07 2011-06-16 Coatex S.A.S. Use of glycerol-containing formulas as agents for assisting the dry grinding of mineral materials
RU2534079C2 (en) * 2009-12-07 2014-11-27 Омиа Интернэшнл Аг Method of classifying mineral substance in presence of glycerol-containing additives, obtained products and their application
EP2330162A1 (en) * 2009-12-07 2011-06-08 Omya Development AG Method for classifying mineral material in the presence of additives containing glycerol, products obtained and uses thereof
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US9163147B2 (en) 2009-12-24 2015-10-20 Coatex S.A.S. Use of glycerol as an agent to improve the self-dispersing properties of a mineral material to be added to an aqueous composition
WO2011077232A1 (en) 2009-12-24 2011-06-30 Coatex Sas Use of glycerol as an agent to improve the self-dispersing properties of a mineral material to be added to an aqueous composition
US10221319B2 (en) 2009-12-24 2019-03-05 Coatex Use of glycerol as an agent to improve the self-dispersing properties of a mineral material to be added to an aqueous composition
WO2014019827A1 (en) * 2012-08-02 2014-02-06 Sika Technology Ag Food grade grinding aid composition
EP2692241A1 (en) * 2012-08-02 2014-02-05 Sika Technology AG Food grade grinding aid composition
US11014858B2 (en) 2016-03-30 2021-05-25 Gcp Applied Technologies Inc. Mineral grinding

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US7887630B2 (en) 2011-02-15
WO2007109328A3 (en) 2008-01-03
CA2677340A1 (en) 2007-09-27
US20100210182A1 (en) 2010-08-19
RU2438786C2 (en) 2012-01-10
BRPI0709339A2 (en) 2011-07-12
US20070221764A1 (en) 2007-09-27
MX2008012079A (en) 2008-11-18
RU2008139998A (en) 2010-04-27
CA2677340C (en) 2014-05-06

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