A. Field of Invention
The present invention is directed generally to a method of production of value-added, biobased chemicals, derivative products, and/or purified glycerin from bioglycerin of recycled oil, grease, and/or fat origin. A method of purification of a crude bioglycerin of recycled oil, grease, and/or fat origin is described herein, which provides methods for desalinating, decolorizing, and/or concentrating a bioglycerin of recycled oil, grease, and/or fat origin for the production of biobased chemicals, derivative products, and/or purified glycerin.
B. Description of the Related Art
The world currently faces depletion of fossil fuels while demands for these fuels are ever increasing. Petrochemicals provide an energy source and a component of the majority of raw materials used in many industries. In fact, approximately 95% of all chemicals manufactured today are derived from petroleum. However, this heavy reliance upon fossil fuels is creating harm to the environment. The burning of these fossil fuels has led to the pollution of air, water and land, as well as global warming and climate changes. Through the use of fossil fuels, the environment has been harmed, perhaps irreparably, in an effort to meet the nearly insatiable demand for energy and manufactured products. Fossil fuels are a finite natural resource, with the depletion of readily available oil reserves across the globe; the supply chain has shifted to more complex and environmentally risky production technologies. A reduction and conservation of fossil fuels is clearly needed. Some alternatives to fossil fuels, like solar power, wind power, geothermal power, hydropower, and nuclear power, are used to a degree. However, a more efficient use of renewable resources is always being sought.
In particular, biofuels, which come from a renewable, carbonaceous source, are targeted to become one of these more efficient resources. In the demand for fossil fuels, biodiesel, a type of biofuel, has emerged as a potentially inexhaustible alternative to petroleum diesel, particularly during an oil crisis, a surge in crude oil prices, and/or political unrest in the oil producing regions of the world. This renewable and clean-burning diesel replacement is said to reduce our dependence on foreign petroleum and create new employment within the green industry.
Biodiesel is considered as an environmentally friendly, renewable transportation and heating fuel relative to petroleum diesel. Biodiesel can be made from recycled plant-based triglycerides of agricultural and/or other plant origin as well as recycled animal-based triglycerides. Some of these recycled products of agricultural origin may include recycled soybean oil, recycled corn oil, recycled cottonseed oil, recycled canola oil, recycled rice bran oil, recycled flax oil, recycled sunflower oil, recycled safflower oil, recycled artichoke oil, recycled sesame oil, and recycled peanut oil. Some of these other recycled products of plant origin may include recycled castor oil, recycled coconut oil, recycled colza oil, recycled false flax oil, recycled hemp oil, recycled mustard oil, recycled palm oil, recycled radish oil, recycled rapeseed oil, recycled tigernut oil, recycled tung oil, recycled copaiba oil, recycled jatropha oil, recycled jojoba oil, recycled karanj oil, recycled milk bush (pencil bush) oil, recycled neem oil, recycled olive oil, recycled salicornia oil, and recycled paradise oil. Biodiesel may also be made from recycled products of animal-based triglycerides. The recycled animal-based triglyceride can come from various animal products, such as recycled meat, recycled meat by-products, recycled animal fat, recycled animal tallow, recycled choice white grease, recycled yellow grease, recycled lard, recycled fish, recycled fish by-products, recycled milk, and/or recycled eggs. The recycled animal-based triglycerides can originate from cattle, pigs, boar, sheep and/or lambs, horses, rabbits, deer, antelope, bison, ox, chickens, turkeys, geese, ducks, quail, ostrich, elk, emu, whales, sharks, dolphins, fish, clams, and mussels. Based on the sources of recycled products of recycled triglycerides for biodiesel, recycled plant-based oil, recycled plant-based grease, and/or recycled plant-based fat, and/or recycled animal-based oil, recycled animal-based grease, and/or recycled animal-based fat may provide renewable means for replacing fossil fuels; this biodiesel may be made from recycled product of recycled oil, grease, and/or fat origin. The recycled product of recycled oil, grease, and/or fat origin may come from recycled plant-based triglyceride products and/or recycled animal-based triglyceride products that may be provided from various sources as this recycled waste product. The various sources for the recycled product of recycled oil, grease, and/or fat origin may include residences, restaurants, cafeterias, schools, hotels, camps, hospitals, food preparation facilities, food processing facilities, and/or other food-based businesses. The recycled product of recycled oil, grease, and/or fat origin may also include waste oils, fats, grease, butter, margarine, lard, and/or shortening. Additional sources of the recycled product of recycled oil, grease and/or fat origin may include renderers, and commercial, industrial, and municipal waste treatment facilities that collect either trap grease and/or brown grease. The recycled product of recycled oil, grease, and/or fat origin from various sources may then be recycled within the process described herein to provide a bioglycerin of recycled oil, grease, and/or fat origin.
Prior to the production of biodiesel, the recycled product of recycled oil, fat, and/or grease origin may require filtration to remove particulates. These particulates may be food particles and/or other particles that have been introduced into the recycled product of recycled oil, fat, and/or grease origin. Depending on the size and/or nature of the particulates, different methods to remove these particulates may be required. Even though the recycled product of recycled oil, fat, and/or grease origin may be recycled to provide biodiesel, the production of biodiesel from the recycled product of recycled oil, fat, and/or grease origin does present a production by-product: a crude bioglycerin of recycled oil, grease, and/or fat origin. Biodiesel from the recycled product of recycled oil, fat, and/or grease origin consists of mono-alkyl esters of long chain fatty acids that are formed by reaction of the triglyceride present in the recycled product of recycled oil, fat, and/or grease origin with an alcohol. This process yields a biodiesel of recycled oil, grease and/or fat origin through a hydrolysis and/or transesterification reaction during which a crude bioglycerin of recycled oil, grease, and/or fat origin is cleaved from the triglyceride as a by-product. Thus, the process yields two products: biodiesel of recycled oil, grease, and/or fat origin and a crude bioglycerin of recycled oil, grease, and/or fat origin. The crude bioglycerin of recycled oil, grease, and/or fat origin is formed in approximately 1 part to each 10 parts of biodiesel of recycled oil, grease, and/or fat origin. In the pure form, glycerin is a colorless, viscous liquid; however, the crude bioglycerin of recycled oil, grease, and/or fat origin may be a yellowish to dark brown to nearly black liquid. It may be a clear to a turbid liquid, or have a syrup-like consistency. Besides solid particulates, the crude bioglycerin of recycled oil, grease, and/or fat origin may contain significant amounts of dissolved inorganic salts, alcohol, water, unreacted fatty acids, and other impurities from the biodiesel process. Because of the high content of these impurities, which can range from about 5% to more than about 30%, uses for the crude bioglycerin of recycled oil, grease, and/or fat origin are limited while escalating global biodiesel production is culminating in a market glut for this by-product. Additionally, varying purity levels of the crude bioglycerin of recycled oil, grease, and/or fat origin due to different feedstock sources of the biodiesel, even among various sources of the recycled product of recycled oil, grease, and/or fat origin, as well as different levels of in-process control among biodiesel producers, do not provide a uniform approach to treating the crude bioglycerin by-product of recycled oil, grease, and/or fat origin. Even if the crude bioglycerin of recycled oil, grease, and/or fat origin is treated, the purification of the crude bioglycerin of recycled oil, grease, and/or fat origin historically has been too expensive and commercial implementation of a purification process for the crude bioglycerin of recycled oil, grease, and/or fat origin is yet to prove economical at large scale.
Because the crude bioglycerin of recycled oil, grease, and/or fat origin can be expensive to purify and market demand for the crude material is limited, it is often sold at a significant discount relative to the price of a petroleum-based glycerin. In lieu of a market outlet, the crude bioglycerin of recycled oil, grease, and/or fat origin would quickly accumulate as an unwanted waste product of biodiesel production from the recycled product of recycled oil, grease, and/or fat origin with associated disposal costs. Although this green process of creating biofuel is grounded upon the sustainable use of renewable resources, the process unfortunately generates a low-value by-product that diminishes the overall green value of biodiesel production. However, a purified bioglycerin of recycled oil, grease, and/or fat origin from the production of this biofuel would provide an even greener process as well as become a potential additional revenue stream for biodiesel producers. Such a purified bioglycerin of recycled oil, grease, and/or fat origin could compete and function as a green replacement to a petroleum-derived glycerin and/or serve as a renewable feedstock for the production of value-added, biobased chemicals, derivative products, and/or purified glycerin.
In the pure form, glycerin has many uses. It is used in the food and beverage industry as a humectant, sweetener, solvent, preservative, filler, emulsifier, and thickening agent. It also has several uses in the personal care and pharmaceutical industries where it functions as a lubricant, humectant, laxative, bacteriostat, moisturizer and pharmaceutical excipient. It is a well-known component of glycerin soaps. It also has applications in tobacco, polyether polyols, alkyd resins, paints, coatings, lubricants, textiles, paper, biological research, fabric softeners, cellophane, explosives, and epoxy resins. Purer forms of a bioglycerin of recycled oil, grease, and/or fat origin also command a higher market value as compared to a less pure bioglycerin of recycled oil, grease, and/or fat origin. Additionally, potential emerging applications for a bioglycerin of recycled oil, grease, and/or fat origin include its conversion into commodity chemicals, like 1,2-propanediol and 1,3-propanediol, and into fine chemicals like epichlorohydrin, glycidyl ethers and glycidyl esters. Once implemented, these applications are expected to further improve global market demand for bioglycerin of recycled oil, grease, and/or fat origin. Overall, a purified bioglycerin of recycled oil, grease, and/or fat origin from recycled oil, grease, and/or fat-based biodiesel production could serve as a feedstock for production of value-added, biobased chemicals, derivative products, and/or purified glycerin, and as a means to reduce costs associated with waste stream disposal.
The present invention provides methods for purifying crude bioglycerin of recycled oil, grease, and/or fat origin and converting crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified-bioglycerin of recycled oil, grease, and/or fat origin into value-added, biobased chemicals, derivative products, and/or purified glycerin while minimizing waste products.
Accordingly, it is an object of the invention to provide a method of biorefining. It may include the steps of providing a crude bioglycerin of recycled oil, grease, and/or fat origin and treating the crude bioglycerin of recycled oil, grease, and/or fat origin through one or more steps of a purification process for crude bioglycerin of recycled oil, grease, and/or fat origin to provide a purified bioglycerin of recycled oil, grease, and/or fat origin. Additionally, the crude bioglycerin of recycled oil, grease, and/or fat origin may be provided from at least one recycled triglyceride provided from a recycled product of recycled plant-based oil, recycled plant-based fat, recycled plant-based grease, recycled plant-based butter, recycled plant-based margarine, recycled plant-based lard, recycled plant-based shortening, recycled animal-based oil, recycled animal-based fat, recycled animal-based grease, recycled animal-based butter, recycled animal-based margarine, recycled animal-based lard, and recycled animal-based shortening. The recycled triglyceride of agricultural and/or other plant origin may include recycled soybean oil, recycled corn oil, recycled cottonseed oil, recycled canola oil, recycled rice bran oil, recycled flax oil, recycled sunflower oil, recycled safflower oil, recycled artichoke oil, recycled sesame oil, recycled peanut oil, recycled castor oil, recycled coconut oil, recycled colza oil, recycled false flax oil, recycled hemp oil, recycled mustard oil, recycled palm oil, recycled radish oil, recycled rapeseed oil, recycled tigernut oil, recycled tung oil, recycled copaiba oil, recycled jatropha oil, recycled jojoba oil, recycled karanj oil, recycled milk bush (pencil bush) oil, recycled neem oil, recycled olive oil, recycled salicornia oil, and recycled paradise oil. The recycled animal-based triglyceride can come from various animal products, such as recycled meat, recycled meat by-products, recycled animal fat, recycled animal tallow, recycled choice white grease, recycled yellow grease, recycled lard, recycled fish, recycled fish by-products, recycled milk, and/or recycled eggs. Moreover, the recycled animal-based triglyceride can originate from cattle, pigs, boar, sheep and/or lambs, horses, rabbits, deer, antelope, bison, ox, chickens, turkeys, geese, ducks, quail, ostrich, elk, emu, whales, sharks, dolphins, fish, clams, and mussels. Furthermore, the crude bioglycerin of recycled oil, grease, and/or fat origin may be provided from at least one recycled product of recycled oil, fat, and/or grease origin provided from residences, restaurants, cafeterias, schools, hotels, camps, hospitals, food preparation facilities, food processing facilities, and other food-based businesses. Additional sources of the recycled product of recycled oil, grease and/or fat origin may include renderers, and commercial, industrial, and municipal waste treatment facilities that collect either trap grease and/or brown grease.
One object of the present invention is that a purified bioglycerin of recycled oil, grease, and/or fat origin may be produced from a by-product of biodiesel production from a recycled product of recycled oil, fat, and/or grease.
Another object of the present invention is that the steps of treating the crude bioglycerin of recycled oil, grease, and/or fat origin to provide a purified bioglycerin of recycled oil, grease, and/or fat origin comprises at least one step of desalination treatment, decolorization treatment, and concentration treatment.
Yet another object of the present invention is that the desalination treatment provides a desalinated bioglycerin of recycled oil, grease, and/or fat origin, the decolorization treatment provides a decolorized bioglycerin of recycled oil, grease, and/or fat origin, and the concentration treatment provides a concentrated bioglycerin of recycled oil, grease, and/or fat origin.
Still another object of the present invention is that the step of treating the crude bioglycerin of recycled oil, grease, and/or fat origin by the desalination treatment to provide a desalinated bioglycerin of recycled oil, grease, and/or fat origin may use an ion exchange treatment.
Yet another object of the present invention is that the step of treating the crude bioglycerin of recycled oil, grease, and/or fat origin to provide a decolorized bioglycerin of recycled oil, grease, and/or fat origin can use a decolorizing treatment process.
Still yet another object of the present invention is that the step of treating the crude bioglycerin of recycled oil, grease, and/or fat origin to provide a concentrated bioglycerin of recycled oil, grease, and/or fat origin may use a concentration treatment process.
Still another object of the present invention is that the steps of the desalination treatment, the decolorization treatment, and the concentration treatment for purification of the crude bioglycerin of recycled oil, grease, and/or fat origin may be performed in any order.
A further object of the present invention is that one or more of the steps of the desalination treatment, the decolorization treatment, and the concentration treatment for purification of the crude bioglycerin of recycled oil, grease, and/or fat origin may be repeated.
Yet another object of the present invention is that one or more of the steps of the desalination treatment, the decolorization treatment, and the concentration treatment for purification of the crude bioglycerin of recycled oil, grease, and/or fat origin can be skipped.
Still yet another object of the present invention is that the desalination treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin may be performed under batch or continuous flow conditions.
According to one embodiment of the present invention, a solvent can be added, recovered and recycled during the desalination treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin.
According to another embodiment of the present invention, the ion exchange resins may be regenerated and recycled during the desalination treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin.
According to still another embodiment of the present invention, the desalination treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin can be low energy demanding.
According to still yet another embodiment of the present invention, the desalination treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin can recover salt, which is useful for commercial de-icing or lowering the freezing point of solutions.
According to still yet another embodiment of the present invention, the desalination treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin produces water that may be recovered and reused.
Still another object of the present invention is that the decolorization treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin may be performed under batch or continuous flow conditions.
According to one embodiment of the present invention, a solvent may be added, recovered and recycled during the decolorization treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin.
According to another embodiment of the present invention, the decolorization treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin may use activated charcoal.
According to still another embodiment of the present invention, the decolorization treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin can be low energy demanding.
According to still yet another embodiment of the present invention, can be the recovery and recycle of the activated charcoal used in the decolorization treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin.
Still another object of the present invention is that the concentration treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin can be performed under batch or continuous flow conditions.
According to one embodiment of the present invention, the concentration treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin can be performed at reduced pressure and modest temperature.
According to another embodiment of the present invention, the concentration treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin can be low energy demanding.
According to yet another embodiment of the present invention, is the recovery and recycle of water and solvent in the concentration treatment step of the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin.
Another object of the present invention is that the yield recovery of a purified bioglycerin of recycled oil, grease, and/or fat origin from the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin may be greater than 80% of the theoretical yield amount of bioglycerin from recycled oil, grease, and/or fat-based biodiesel production.
Yet another object of the present invention is the yield recovery of a purified bioglycerin of recycled oil, grease, and/or fat origin from the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin can be greater than 90% of the theoretical yield amount of bioglycerin from recycled oil, grease, and/or fat-based biodiesel production.
Another object of the present invention is that the weight of a purified bioglycerin of recycled oil, grease, and/or fat origin from the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin may be greater than 60% of the weight of the crude bioglycerin produced from recycled oil, grease, and/or fat origin.
Still another object of the present invention is that the weight of a purified bioglycerin of recycled oil, grease, and/or fat origin from the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin may be greater than 80% of the weight of the crude bioglycerin produced from recycled oil, grease, and/or fat origin.
Still yet another object of the present invention is that the weight of a purified bioglycerin of recycled oil, grease, and/or fat origin from the purification process for crude bioglycerin of recycled oil, grease, and/or fat origin can be greater than 90% of the weight of the crude bioglycerin produced from recycled oil, grease, and/or fat.
Still yet another object of the present invention can be the steps of producing one or more of the biobased chemicals, derivative products, and/or purified glycerin from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin.
According to one embodiment of the present invention, purified bioglycerins of recycled oil, grease, and/or fat origin of different purities can produce one or more of the biobased chemicals, derivative products, and/or purified glycerin.
According to another embodiment of the present invention, the production of the biobased chemicals and/or derivative products from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin may take place by a chemical process.
According to still another embodiment of the present invention, the production of the biobased chemicals and/or derivative products from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin may take place by a biological process.
According to yet another embodiment of the present invention, the production of the biobased chemicals and/or derivative products from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin may take place by a catalytic process.
According to still yet another embodiment of the present invention, the production of the biobased chemicals and/or derivative products from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin may take place by pyrolytic process.
According to yet another embodiment of the present invention, the production of the biobased chemicals and/or derivative products from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin can involve one or more the chemical, biological, catalytic, or pyrolysis processes.
Further, another object of the present invention can be functionalizing the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin to form a functionalized bioglycerin product of recycled oil, grease, and/or fat origin prior to the production of the biobased chemicals and/or derivative products.
According to another aspect, the present invention can provide for the production of a plurality of the biobased chemicals and/or derivative products from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin comprising but not limited to purified glycerin, glycerin derivatives, C1-C3 alcohols, C2/C3 diols, C1-C3 aldehydes/ketones, C1-C3 carboxylic acids, C1-C3 esters of C1-C3 carboxylic acids, C5/C6 polyols, polyol derivatives, glycidol, glycidyl derivatives, glyceraldehyde, glyceraldehyde derivatives, and epihalohydrins.
According to yet another aspect, the present invention can provide for the production of a plurality of biobased chemicals and/or derivative products from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin, comprising but not limited to purified glycerin, methanol, ethanol, n-propanol, isopropanol, allyl alcohol, propargyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, formaldehyde, acetaldehyde, propionaldehyde, glyoxal, acrolein, acetone, 1-hydroxyacetone, 1,3-dihydroxyacetone, formic acid, acetic acid, glycolic acid, glyoxylic acid, oxalic acid, propionic acid, lactic acid, 2,3-dihydroxypropionic acid, pyruvic acid, acrylic acid, malonic acid, hydroxymalonic acid, methyl formate, methyl acetate, methyl glycolate, methyl glyoxylate, dimethyl oxalate, methyl propionate, methyl lactate, methyl 2,3-dihydroxypropionate, methyl pyruvate, methyl acrylate, dimethyl malonate, dimethyl hydroxymalonate, ethyl formate, ethyl acetate, ethyl glycolate, ethyl glyoxylate, diethyl oxalate, ethyl propionate, ethyl lactate, ethyl 2,3-dihydroxypropionate, ethyl pyruvate, ethyl acrylate, diethyl malonate, diethyl hydroxymalonate, n-propyl formate, n-propyl acetate, n-propyl glycolate, n-propyl glyoxylate, di-n-propyl oxalate, n-propyl propionate, n-propyl lactate, n-propyl 2,3-dihydroxypropionate, n-propyl pyruvate, n-propyl acrylate, di-n-propyl malonate, di-n-propyl hydroxymalonate, isopropyl formate, isopropyl acetate, isopropyl glycolate, isopropyl glyoxylate, diisopropyl oxalate, isopropyl propionate, isopropyl lactate, isopropyl 2,3-dihydroxypropionate, isopropyl pyruvate, isopropyl acrylate, diisopropyl malonate, diisopropyl hydroxymalonate, allyl formate, allyl acetate, allyl glycolate, allyl glyoxylate, diallyl oxalate, allyl propionate, allyl lactate, allyl 2,3-dihydroxypropionate, allyl pyruvate, allyl acrylate, diallyl malonate, diallyl hydroxymalonate, glycerol formal, 4-(hydroxymethyl)-1,3-dioxolan-2-one, 4-methyl-1,3-dioxolane, (2,2-dimethyl-1,3-dioxolan-4-yl)methanol, 1,4-dioxaspiro[4.5]decane-2-methanol, glyceraldehyde, 2,2-dimethyl-1,3-dioxolane-4-carbaldehyde, 1,4-dioxaspiro[4.5]decane-2-carbaldehyde, glycidol, glycidyl methyl ether, glycidyl ethyl ether, glycidyl n-propyl ether, glycidyl isopropyl ether, glycidyl n-butyl ether, glycidyl isobutyl ether, glycidyl sec-butyl ether, glycidyl tert-butyl ether, glycidyl allyl ether, glycidyl propargyl ether, glycidyl hexadecyl ether, glycidyl octyl/decyl ether, glycidyl phenyl ether, glycidyl benzyl ether, glycidyl formate, glycidyl acetate, glycidyl propionate, glycidyl isopropionate, glycidyl n-butyrate, glycidyl isobutyrate, glycidyl sec-butyrate, glycidyl acrylate, glycidyl methacrylate, diglycidyl 1,2-cyclohexanedicarboxylate, glycidyl benzoate, glycidyl 4-nitrobenzoate, epichlorohydrin, epibromohydrin, ribitol, arabitol, xylitol, mannitol, sorbitol, galactitol, allitol, iditol, and bis-(2,2-dimethyl-(1,3)dioxolan-4-yl methanol.
Still yet another object of the present invention is the plurality of biobased chemicals and/or derivative products produced from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin comprises at least one of achiral, racemic, and optically pure products.
Still another object of the present invention is that at least one of the biobased chemicals and/or derivative products produced from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin can be used in the production of other chemicals, materials, and products.
Another object of the present invention is at least one of the biobased chemicals and/or derivative products produced from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin comprises at least one of commodity chemicals, fine chemicals, and/or specialty chemicals.
Yet another object of the present invention is that it can provide a method of biorefining, comprising the steps of providing a crude bioglycerin of recycled oil, grease, and/or fat origin, treating the crude bioglycerin of recycled oil, grease, and/or fat origin by one or more desalination treatment, decolorization treatment and concentration treatment steps to provide a purified bioglycerin of recycled oil, grease, and/or fat origin, and producing a plurality of biobased chemicals, derivative products, and/or purified glycerin from the crude bioglycerin of recycled oil, grease, and/or fat origin and/or a purified bioglycerin of recycled oil, grease, and/or fat origin.
Still another object of the present invention is that it can provide a method of biorefining. It may include the steps of providing a crude bioglycerin of recycled oil, grease, and/or fat origin and treating the crude bioglycerin of recycled oil, grease, and/or fat origin to provide a purified bioglycerin of recycled oil, grease, and/or fat origin. The method may further include recovering and using the salts, water, and alcohol contaminating the crude bioglycerin of recycled oil, grease, and/or fat origin from the recycled oil, grease, and/or fat-based biodiesel production process.
Yet another object of the present invention is that it can provide a method of biorefining. It may include the steps of providing a crude bioglycerin of recycled oil, grease, and/or fat origin and treating the crude bioglycerin of recycled oil, grease, and/or fat origin to provide a purified bioglycerin of recycled oil, grease, and/or fat origin. The method may further include recovering and using any solvents used in the purification of the crude bioglycerin of recycled oil, grease, and/or fat origin.
Still yet another object of the present invention is that it may provide a method of providing a crude bioglycerin of recycled oil, grease, and/or fat origin and treating the crude bioglycerin of recycled oil, grease, and/or fat origin to provide a purified bioglycerin of recycled oil, grease, and/or fat origin where the waste product from the purified bioglycerin of recycled oil, grease, and/or fat origin process can be used to produce energy.
Further, another object of the present invention can be to provide a method for biorefining that is easy to implement and use.
Still other benefits and advantages of the invention will become apparent to those skilled in the art to which it pertains upon a reading and understanding of the following detailed specification.
The invention may take physical form in certain parts and arrangement of parts, embodiments of which will be described in detail in this specification and illustrated in the accompanying drawings which form a part hereof, and wherein:
Referring now to the drawings wherein the showings are for purposes of illustrating embodiments of the invention only and not for purposes of limiting the same. Relative language used herein is best understood with reference to the drawings, in which like numerals are used to identify like or similar items.
The crude bioglycerin of recycled oil, grease, and/or fat origin 10 is a by-product of biodiesel production 60, through the hydrolysis and/or transesterification process used in the manufacture of biodiesel 62. Biodiesel production 60 from a recycled product of recycled oil, fat, and/or grease origin yields mostly biodiesel 62, with roughly 10% of the product mass being a crude bioglycerin of recycled oil, grease, and/or fat origin 10. Escalating biodiesel production 60 across the globe is generating large quantities of crude bioglycerin of recycled oil, grease, and/or fat origin 10 that could be used in the production of a purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or the production of biobased chemicals 50. Additionally, the crude bioglycerin of recycled oil, grease, and/or fat origin 10 may come from various sources. The crude bioglycerin of recycled oil, grease, and/or fat origin 10 may be provided from a recycled product of recycled oil, fat, and/or grease origin and treating the crude bioglycerin of recycled oil, grease, and/or fat origin 10 through one or more steps of a purification process for crude bioglycerin of recycled oil, grease, and/or fat origin to provide a purified bioglycerin of recycled oil, grease, and/or fat origin 40. Additionally, the crude bioglycerin of recycled oil, grease, and/or fat origin 10 may be provided from at least one recycled triglyceride provided from a recycled product of recycled plant-based oil, recycled plant-based fat, recycled plant-based grease, recycled plant-based butter, recycled plant-based margarine, recycled plant-based lard, recycled plant-based shortening, recycled animal-based oil, recycled animal-based fat, recycled animal-based grease, recycled animal-based butter, recycled animal-based margarine, recycled animal-based lard, and recycled animal-based shortening. The recycled triglyceride of agricultural and/or other plant origin may comprise but is not limited to recycled soybean oil, recycled corn oil, recycled cottonseed oil, recycled canola oil, recycled rice bran oil, recycled flax oil, recycled sunflower oil, recycled safflower oil, recycled artichoke oil, recycled sesame oil, recycled peanut oil, recycled castor oil, recycled coconut oil, recycled colza oil, recycled false flax oil, recycled hemp oil, recycled mustard oil, recycled palm oil, recycled radish oil, recycled rapeseed oil, recycled tigernut oil, recycled tung oil, recycled copaiba oil, recycled jatropha oil, recycled jojoba oil, recycled karanj oil, recycled milk bush (pencil bush) oil, recycled neem oil, recycled olive oil, recycled salicornia oil, and recycled paradise oil. The recycled animal-based triglyceride can come from various animal products comprised of but not limited to recycled meat, recycled meat by-products, recycled animal fat, recycled animal tallow, recycled choice white grease, recycled yellow grease, recycled lard, recycled fish, recycled fish by-products, recycled milk, and/or recycled eggs. Moreover, the recycled animal-based triglyceride can originate from cattle, pigs, boar, sheep and/or lambs, horses, rabbits, deer, antelope, bison, ox, chickens, turkeys, geese, ducks, quail, ostrich, elk, emu, whales, sharks, dolphins, fish, clams, and mussels. Additional sources of the recycled product of recycled oil, grease and/or fat origin may include renderers, and commercial, industrial, and municipal waste treatment facilities that collect either trap grease and/or brown grease. The crude bioglycerin from recycled oil, grease, and/or fat 10 may be provided from at least one recycled product of recycled oil, fat, and/or grease origin provided from residences, restaurants, cafeterias, schools, hotels, camps, hospitals, food preparation facilities, food processing facilities, other food-based businesses, renderers, and commercial, industrial, and municipal waste treatment facilities.
The crude bioglycerin of recycled oil, grease, and/or fat origin 10 can contain several impurities from the hydrolysis and/or transesterification process used in the manufacture of biodiesel 62. Such impurities can include water and an alcohol like methanol or ethanol, with methanol the more typical alcohol impurity. The presence of an alcohol in the crude bioglycerin of recycled oil, grease, and/or fat origin 10 may be due to the fact that an excess of this alcohol can be used to drive the hydrolysis and/or transesterification process of biodiesel production 60 to completion. Also, different biodiesel manufacturers may recover the excess alcohol to varying extents, leading to an inconsistent crude bioglycerin of recycled oil, grease, and/or fat origin 10. In addition to the alcohol and water impurities, the crude bioglycerin of recycled oil, grease, and/or fat origin 10 may contain dissolved salts, like sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, calcium chloride, and calcium sulfate. These salts may arise from neutralization of the transesterification and/or hydrolysis process used in biodiesel production 60. Furthermore, the crude bioglycerin of recycled oil, grease, and/or fat origin 10 may contain residual fatty acids and other impurities leading to color. These impurities may result from either an incomplete process of biodiesel production 60 or from contaminants in the recycled product of recycled oil, grease, and/or fat origin entering the refinery. The levels of water and alcohol contamination in the crude bioglycerin of recycled oil, grease, and/or fat origin 10 may be controlled by evaporation/distillation or by implementing tighter control of the biodiesel processing parameters. However, the salts, which may amount to about 4-10% of the total impurities in the crude bioglycerin of recycled oil, grease, and/or fat origin 10, can be more challenging to remove. Further these salts may impede transformations of the crude bioglycerin of recycled oil, grease, and/or fat origin 10 into the purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or the production of biobased chemicals 50.
Because of these impurities, there may be a limited market demand for the crude bioglycerin of recycled oil, grease, and/or fat origin 10 and the market that does exist often may command a price as low as 1/10th that of a petroleum-derived glycerin. The reason for this limited demand may be that these impurities, and in particular the salts, may severely hamper or restrict uses of the crude bioglycerin of recycled oil, grease, and/or fat origin 10. Historically, the purification of the crude bioglycerin of recycled oil, grease, and/or fat origin 10, and in particular the removal of the salt impurities, has proven too expensive for commercial implementation. For example, the purification of the crude bioglycerin of recycled oil, grease, and/or fat origin 10 by distillation can be a very energy demanding process because the boiling point of glycerin is 290° C. (554° F.). However, the purification process illustrated in
During biodiesel production 60, the crude bioglycerin of recycled oil, grease, and/or fat origin 10 may have an inconsistent appearance or impurity profile from batch to batch or from producer to producer. These differences in appearance or impurity profile may be associated with the characteristics of different recycled products of recycled oil, grease, and/or fat origin coming into these biodiesel facilities, and/or differences in the processes and manufacturing controls used across different biodiesel facilities. The crude bioglycerin of recycled oil, grease, and/or fat origin 10 obtained from biodiesel production 60 can appear as a golden or slightly yellow liquid, or a dark brown substance to blackish liquid that may have a liquid to a syrup-like character. The crude bioglycerin of recycled oil, grease, and/or fat origin 10 can be translucent or turbid in appearance. Depending on the condition of the crude bioglycerin of recycled oil, grease, and/or fat origin 10, several steps within the process of
Depending on the condition of the crude bioglycerin of recycled oil, grease, and/or fat origin 10, it may need to be subjected to the desalination treatment 12, the decolorization treatment 22, and/or the concentration treatment 32. These processing treatments required for purifying the crude bioglycerin of recycled oil, grease, and/or fat origin 10 depend on the end product requirements for the purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or the raw material specification requirements for the production of biobased chemicals 50 from a purified bioglycerin of recycled oil, grease, and/or fat origin 40.
For instance, if the crude bioglycerin of recycled oil, grease, and/or fat origin 10 from the biodiesel production 60 requires desalination, it may undergo the desalination treatment 12 to become a desalinated bioglycerin of recycled oil, grease, and/or fat origin 20. Because these salt impurities can interfere with the purified bioglycerin of recycled oil, grease, and/or fat origin 40 in the production of biobased chemicals 50, the desalination treatment 12 step is used to remove these impurities in order to provide a desalinated bioglycerin of recycled oil, grease, and/or fat origin 20. The desalination treatment 12 step is further detailed in
The crude bioglycerin of recycled oil, grease, and/or fat origin 10, the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20, and/or the decolorized bioglycerin of recycled oil, grease, and/or fat origin 30 may then undergo the concentration treatment 32 wherein further the alcohol and water impurities are removed to provide a concentrated bioglycerin of recycled oil, grease, and/or fat origin 38. The concentration treatment 32 step is detailed in
Within the overall process of converting the crude bioglycerin of recycled oil, grease, and/or fat origin 10 into a purified bioglycerin of recycled oil, grease, and/or fat origin 40, and/or potentially further into production of biobased chemical products 50, several steps may be omitted if the crude bioglycerin of recycled oil, grease, and/or fat origin 10 does not require the desalination treatment 12, the decolorization treatment 22, and/or the concentration treatment 32 to achieve the end product specification for a purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or for the production of biobased chemicals 50. Depending on the condition of the intermediate bioglycerin product of recycled oil, grease, and/or fat origin during any step of the process shown in
After the desalination treatment 12, the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 may be sufficiently treated to become a purified bioglycerin of recycled oil, grease, and/or fat origin 40 if the specification requirements are met for a purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or for the production of biobased chemicals 50. Alternatively, if additional processes are needed for the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 but not the decolorization treatment 22, then the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 may be sent to the concentration treatment 32 where it becomes a concentrated bioglycerin of recycled oil, grease, and/or fat origin 38, which can be used for the conversion to a purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or be sent for the production of biobased chemicals 50.
Additionally, the concentrated bioglycerin of recycled oil, grease, and/or fat origin 38 may also be processed to a purified bioglycerin of recycled oil, grease, and/or fat origin 40, or undergo either the desalination treatment 12 or the decolorization treatment 22 before it can be used for the conversion to a purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or be sent for the production of biobased chemicals 50.
One detail to note during these processes is that the summary of the pathway shown in
Also, any of the process treatment steps like the desalination treatment 12, the decolorization treatment 22, or the concentration treatment 32, may be repeated to provide the requirements for a purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or the production of biobased chemicals 50.
Furthermore, any of the process treatment steps like the desalination treatment 12, the decolorization treatment 22, or the concentration treatment 32, may be conducted under batch or flow conditions for the production of a purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or the production of biobased chemicals 50.
The processing outlined in
The processing outlined in
First, the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 may be received. The high salt bioglycerin of recycled oil, grease, and/or fat origin 14 can originate from the crude bioglycerin of recycled oil, grease, and/or fat origin 10, a decolorized bioglycerin of recycled oil, grease, and/or fat origin 30 and/or a concentrated bioglycerin of recycled oil, grease, and/or fat origin 38. The high salt bioglycerin of recycled oil, grease, and/or fat origin 14 may then undergo the anion exchange treatment 16. The anion exchange treatment 16 step can serve to reduce or remove the anionic impurities present in the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 by use of an anion exchange resin, which exchanges the negatively charged ions of the salt impurities in the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 with the counterion bound to the resin. For instance, this anion exchange treatment 16 may remove halide, sulfate, and other anions first from the high salt bioglycerin the recycled oil, grease, and/or fat origin 14 and replace those anions with hydroxide anions. Through the anion exchange treatment 16, the anionic components of the salt impurities can be removed from the high salt bioglycerin of recycled oil, grease, and/or fat origin 14. After the anion exchange treatment 16 step is completed, the cation exchange treatment 18 step may then occur to reduce and replace the cations from the salt impurities present in the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 with the counterion bound to the cation exchange resin, typically a proton. Through the cation exchange treatment 18, the cationic components of the salt impurities may be reduced and removed from the high salt bioglycerin of recycled oil, grease, and/or fat origin 14. For example, this cation exchange treatment 18 may remove sodium, potassium, calcium, and other cations and replace those cations with protons. Therefore, through both anion and cation exchange treatment steps, the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 can be reduced in levels of both positively and negatively charged ionic salt impurities, and the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 may now be formed. The desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 may then go through one or more additional treatments of decolorization, concentration, and/or transfer to the production of plant-based biobased chemicals 50 as described in
Although the desalination treatment 12 in which the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 is transformed into a desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 can be achieved by first subjecting the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 to the anion exchange treatment 16 step and following that step with the cation exchange treatment 18 step, the process is not limited to this order of ion exchange treatments. Instead, the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 can first undergo the cation exchange treatment 18, and then followed by the anion exchange treatment 16. In other words, either ion exchange treatment can be used first.
Alternatively, the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 can undergo only one of the exchange treatments, either the anion exchange treatment 16 or the cation exchange treatment 18. Depending on the condition of the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 or the conditions required for the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20, the anion exchange treatment 16 or the cation exchange treatment 18 can be omitted.
Alternatively, an amphoteric exchange treatment could be used instead wherein both the anion exchange treatment 16 and the cation exchange treatment 18 occur at once. This type of amphoteric exchanger will exchange both cations and anions simultaneously. Instead of completing two different steps where the anion exchange treatment 16 step and the cation exchange treatment 18 step are separate, a process where all of the ion exchanging can occur in a condensed step may also be used.
Moreover in the course of the desalination treatment 12, each of the steps of the anion exchange treatment 16 and the cation exchange treatment 18 may be conducted more than one time. Repeating the anion exchange treatment 16 step and/or the cation exchange treatment 18 step can allow for applications wherein the levels of dissolved salts in the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 may be further reduced, especially if required for certain specifications of intended product use.
The reduction in levels of both positively and negatively charged ions in the desalination treatment 12 may lead to the formation of a desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 since the salt impurities are reduced or removed by the ion exchange treatment or process. With the desalination treatment 12 of high salt bioglycerin of recycled oil, grease, and/or fat origin 14, both the possibility of creating value-added products and the prevention of a costly waste stream may provide incentives for utilizing the desalination treatment 12 process.
In
Ion exchange resins are classified as cation exchangers, on which positively charged mobile ions are available for exchange, and anion exchangers, on which the exchangeable ions are negatively charged. Both anion exchange resins and cation exchange resins may be produced from the same basic organic polymers. These resin types differ in the ionic functional group attached to the organic polymer network. It is this ionic functional group that determines the chemical behaviour of the resin. Ion exchange resins can be broadly classified as strong or weak acid cation exchangers, or strong or weak base anion exchangers. Ion exchange resins are insoluble substances containing loosely bound counterions that are able to be exchanged with other ions in solutions that come into contact with the resin. These exchanges take place without any physical alteration to the ion exchange material other than the exchange of the loosely bound counterions.
For the anion exchange treatment 16 and the cation exchange treatment 18 of the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 shown in
Returning now to
For
The batch purification method outlined in
The batch cation exchange treatment 90 may then occur after the anion exchange treatment(s). In a cation exchange resin treatments, the resin may reduce or remove sodium, potassium, calcium, and other cations from the impurities present in the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 and replace those cations by the counterion bound to the cation exchange resin, typically protons. The high salt bioglycerin of recycled oil, grease, and/or fat origin 14 may then undergo a second and third cation exchange, the batch cation exchange treatment 92 and the batch cation exchange treatment 94. Like the anion exchange treatment process, the purpose of second and third batch cation exchange treatments can be to further reduce the respective cation levels of the product to specification for a desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 and/or a purified bioglycerin of recycled oil, grease, and/or fat origin 40 for the production of biobased chemicals 50. Depending on the resin, the cation exchange resin can be regenerated with aqueous mineral acids like aqueous hydrochloric acid or aqueous sulfuric acid, as detailed further in
Besides the resin regeneration that provides a greener and less costly means of desalinating the high salt bioglycerin of recycled oil, grease, and/or fat origin 14, the batch purification method of
In
First, the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 may be received in the continuous flow purification method for the desalination treatment 12. The high salt bioglycerin of recycled oil, grease, and/or fat origin 14 can originate from a crude bioglycerin of recycled oil, grease, and/or fat origin 10, a decolorized bioglycerin of recycled oil, grease, and/or fat origin 30, and/or a concentrated bioglycerin of recycled oil, grease, and/or fat origin 38. As the crude bioglycerin of recycled oil, grease, and/or fat origin 10, the decolorized bioglycerin of recycled oil, grease, and/or fat origin 30, and/or the concentrated bioglycerin of recycled oil, grease, and/or fat origin 38 may be brought together as the high salt bioglycerin of recycled oil, grease, and/or fat origin 14; an optional solvent addition 8 can be done. This optional solvent addition 8 can be water, an alcohol, an alcohol/water mixture, or other solvent in which the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 may be miscible. The optional solvent addition 8 may typically be an alcohol like methanol, but may also be ethanol. This optional solvent addition 8 serves to reduce the viscosity of the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 and helps enhance recovery of the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20 from the ion exchange resins. Solvents used in the optional solvent addition 8 may be recovered in the concentration treatment 32, as shown in
Like the batch purification method in
The general flow outlined in
Optionally, a reduced anion bioglycerin of recycled oil, grease, and/or fat origin 88 may be obtained from the flow anion exchange treatment 86, which may be subjected to one or more cycle(s) of the flow anion exchange treatment 86. These treatments are optional cycle(s) of flow anion exchange where the reduced anion bioglycerin of recycled oil, grease, and/or fat origin 88 can be sent through the flow exchange column again to further reduce anion levels to the desired specifications for the production of the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20, and/or a purified bioglycerin of recycled oil, grease, and/or fat origin 40 and/or be sent for the production of biobased chemicals 50.
Also, the reduced cation bioglycerin of recycled oil, grease, and/or fat origin 98 may be optionally subjected to one or more cycle(s) of the flow cation exchange treatment 96 in order to meet the cation levels to the desired specifications for the production of the desalinated bioglycerin of recycled oil, grease, and/or fat origin 20, and/or a purified bioglycerin of recycled oil, grease, and/or fat origin 40 for the production of biobased chemicals 50. Like the optional cycle(s) of the flow anion exchange treatment 86 of the reduced anion bioglycerin of recycled oil, grease, and/or fat origin 88, the reduced cation bioglycerin of recycled oil, grease, and/or fat origin 98 can be subjected to optional cycle(s) of the flow cation exchange treatment 96.
Depending upon the resin, the anion exchange resin can be regenerated with an alkali base like aqueous sodium hydroxide, aqueous potassium hydroxide, or aqueous ammonia, and the cation exchange resin can be regenerated with aqueous mineral acids like aqueous hydrochloric acid or aqueous sulfuric acid after the continuous flow exchange process. Besides the resin regeneration providing a greener and less costly means of desalinating the high salt bioglycerin of recycled oil, grease, and/or fat origin 14, the continuous flow purification method of
One of the advantages of using an ion exchange treatment or process to desalinate the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 for other applications can be that the treatment or process itself can generate little to no waste. Another advantage may be that the ion exchange resins used in the ion exchange treatment or process can be regenerated and recycled. In other words, the ion exchange resins can be used multiple times, providing a greener process with fewer waste products and minimizing costs with purchasing new ion exchange resins.
The exchange resin regeneration 118 is detailed further in
In
Ion exchange resins are polymers that are capable of exchanging particular ions within the polymer with ions within a solution that is passed through the ion exchange resins. This can occur for anion resin exchangers in the flow anion exchange treatment 86 and for cation exchange resins in the flow cation exchange treatment 96 of
There are two types of ion exchange resins used in the continuous flow process. The first may be an anion exchange resin and the second may be a cation exchange resin. Whether the anion exchange resin or the cation exchange resin may be used, the regeneration process can be similar. Although the anion exchange resin and the cation exchange resin may be processed similarly, each ion exchange resin can be separately regenerated.
After acting to desalinate the high salt bioglycerin of recycled oil, grease, and/or fat origin 14 of
For the anion exchange resin regeneration, typically an aqueous alkali 100 may be added to the anion exchange resin in the saturated anion exchange resin column 102. In this process, the regenerated anion exchange resin column 104 will be formed along with an aqueous inorganic salt 112. Typically, this aqueous alkali 100 can be aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous ammonia, or another source of aqueous hydroxide anion that may be compatible with the anion exchange resin. From the regenerated anion exchange resin column 104, the anion exchange resin can be reused after it is directed back to the flow anion exchange treatment 86.
Alternatively in the cation exchange resin regeneration, an aqueous mineral acid 106 can be added to the cation exchange resin in the saturated cation exchange resin column 108, and the regenerated cation exchange resin column 110 may be formed along with an aqueous inorganic salt 112. Typically, this aqueous mineral acid 106 can be aqueous hydrochloric acid or aqueous sulfuric acid, with aqueous sulfuric acid being the less expensive option and could be used to keep costs down. Depending on compatibility with the cation exchange resin, certain other protic acids may be used in the regenerated cation exchange resin column 110. After this regeneration process in the regenerated cation exchange resin column 108, the cation exchange resin can be reused after it is directed back to the flow cation exchange treatment 96.
Besides the regeneration of both the anion and cation exchange resins, the process can also provide the recovered water 114 and the recovered inorganic salt 116. After both the flow anion exchange treatment 86 and the flow cation exchange treatment 96, an aqueous inorganic salt 112 may be formed in the saturated anion exchange resin column 102 and the saturated cation exchange resin column 108. Instead of initiating another waste stream, this aqueous inorganic salt 112 salt can generate yet another profitable chemical source and/or prevent disposal of another waste stream. A separation of the recovered water 114 and the recovered inorganic salt 116 can be achieved through evaporation or distillation of the water, reverse osmosis, ion exchange, or by crystallization of the salt from a saturated solution. The recovered salt may be sold for industrial applications such as road salt, chilling salts, or the like. In some cases, the salt formed during this phase may also be recovered for use as fertilizer or as a material for lowering the freezing point. Other potential applications may also include water softening, food additives, de-icing, and the production of pharmaceuticals and other chemicals.
After the water is removed from the aqueous inorganic salt 112 as the recovered water 114, it can either be safely added to the wastewater system or it could be recycled and reused elsewhere in the desalination process of
After the colored bioglycerin of recycled oil, grease, and/or fat origin 120 is collected, it may undergo an optional solvent addition 8. Like the optional solvent addition 8 in the desalination treatment 12 shown in
With or without the optional solvent addition 8, the colored bioglycerin of recycled oil, grease, and/or fat origin 120 may then be subjected to the charcoal treatment 122. If it is used, the charcoal treatment 122 serves to reduce or remove color and improve the clarity of the resulting decolorized bioglycerin of recycled oil, grease, and/or fat origin 30. The charcoal treatment 122 may work primarily by an adsorption mechanism. Adsorption is the adhesion of solid materials or dissolved materials onto a surface based on surface energy. During the charcoal treatment 122, the level of residual fatty acids and colored impurities present in colored bioglycerin of recycled oil, grease, and/or fat origin 120 can be reduced or removed by adhesion onto an adsorbent, typically activated charcoal. That is, the charcoal treatment 122 may be a more selective adsorption method for removal of these impurities than it can be for the decolorized bioglycerin of recycled oil, grease, and/or fat origin 30. The colored impurities may adhere to the activated charcoal adsorbent used in the charcoal treatment 122. This charcoal treatment 122 may provide a lighter colored to a nearly clear decolorized bioglycerin of recycled oil, grease, and/or fat origin 30. Depending upon the stage of the purification process of
Furthermore, a reduction in the level of residual fatty acid and colored impurities in the colored bioglycerin of recycled oil, grease, and/or fat origin 120 can be additionally controlled depending on the number of charcoal treatment(s) 122 or process. Depending on the intended use of the decolorized bioglycerin of recycled oil, grease, and/or fat origin 30, the charcoal treatment 122 may have a variety of different processing methods. These methods may include the additional step of repeating cycles of the charcoal treatment 122 of the color treated bioglycerin of recycled oil, grease, and/or fat origin 124. The optional charcoal treatment 122 and the number of its repeating cycles can depend on the color of the colored bioglycerin of recycled oil, grease, and/or fat origin 120 and level of the colored impurities. However, a more decolorized bioglycerin of recycled oil, grease, and/or fat origin 30 may require increased energy and costs associated with additional cycles of charcoal treatment(s) 122.
After the desired color of the color treated bioglycerin of recycled oil, grease, and/or fat origin 124 may be achieved through the charcoal treatment(s) 122, the color treated bioglycerin of recycled oil, grease, and/or fat origin 124 can move to a decolorized bioglycerin of recycled oil, grease, and/or fat origin 30. The resulting decolorized bioglycerin of recycled oil, grease, and/or fat origin 30 may be sent to the desalination treatment 12, or the concentration treatment 32, or can become a purified bioglycerin of recycled oil, grease, and/or fat origin 40 for the production of biobased chemicals 50 as illustrated in
In
The concentration treatment 32 may be done on the crude bioglycerin of recycled oil, grease, and/or fat origin 10, a desalinated bioglycerin of recycled oil, grease, and/or fat origin 20, and/or a decolorized bioglycerin of recycled oil, grease, and/or fat origin 30. At least one of the crude bioglycerin of recycled oil, grease, and/or fat origin 10, a desalinated bioglycerin of recycled oil, grease, and/or fat origin 20, and/or a decolorized bioglycerin of recycled oil, grease, and/or fat origin 30 can be brought into the treatment as the diluted bioglycerin of recycled oil, grease, and/or fat origin 130.
With the concentration treatment 32, the diluted bioglycerin of recycled oil, grease, and/or fat origin 130 may undergo the evaporator/concentrator treatment 132 to produce the concentrated bioglycerin of recycled oil, grease, and/or fat origin 38 and/or the recovered alcohol and water 134. In the evaporator/concentrator treatment 132, the lower boiling alcohol and water impurities can be separated from the diluted bioglycerin of recycled oil, grease, and/or fat origin 130 under reduced pressure and modest temperatures. When the alcohol is methanol or ethanol, these temperatures may be about 25° C. to about 60° C. These reduced pressures may be about 20 mm Hg to about 70 mm Hg. These temperatures may also be higher or the pressures further reduced depending upon the material and equipment capabilities and requirements. By using this concentration treatment 32, the recovered alcohol and water 134 may be removed from the diluted bioglycerin of recycled oil, grease, and/or fat origin 130 and the resulting concentrated bioglycerin of recycled oil, grease, and/or fat origin 38 may be further processed by the desalination treatment 12, or the decolorization treatment 22, and/or be sent to a purified bioglycerin of recycled oil, grease, and/or fat origin 40 for the production of biobased chemicals 50 as shown in
Similarly with the concentration treatment 32, the diluted bioglycerin of recycled oil, grease, and/or fat origin 130 may undergo the evaporator/concentrator treatment 132 to remove solvent from the diluted bioglycerin of recycled oil, grease, and/or fat origin 130 which may be added during the desalination treatment 12 and/or the decolorization treatment 22 steps of the purification process in
From the production of biobased chemicals 50, either with or without the optional functionalization process 140, commodity chemicals 144, fine chemicals 146, and/or specialty chemicals 148 may be produced. Several of these commodity chemicals 144, fine chemicals 146, and/or specialty chemicals 148 may be those shown in
The product categories of the end products from the production of biobased chemicals 50 may include but are not limited to purified glycerin, glycerin derivatives, C1-C3 alcohols, C2/C3 diols, C1-C3 aldehydes/ketones, C1-C3 carboxylic acids, C1-C3 esters of C1-C3 carboxylic acid, C5/C6 polyols, polyol derivatives, glycidol, glycidyl derivatives, glyceraldehyde, glyceraldehyde derivatives, and epihalohydrins. Thereunder the production of biobased chemicals 50, a plurality of specific chemicals can be made comprising but not limited to purified glycerin, methanol, ethanol, n-propanol, isopropanol, allyl alcohol, propargyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, formaldehyde, acetaldehyde, propionaldehyde, glyoxal, acrolein, acetone, 1-hydroxyacetone, 1,3-dihydroxyacetone, formic acid, acetic acid, glycolic acid, glyoxylic acid, oxalic acid, propionic acid, lactic acid, 2,3-dihydroxypropionic acid, pyruvic acid, acrylic acid, malonic acid, hydroxymalonic acid, methyl formate, methyl acetate, methyl glycolate, methyl glyoxylate, dimethyl oxalate, methyl propionate, methyl lactate, methyl 2,3-dihydroxypropionate, methyl pyruvate, methyl acrylate, dimethyl malonate, dimethyl hydroxymalonate, ethyl formate, ethyl acetate, ethyl glycolate, ethyl glyoxylate, diethyl oxalate, ethyl propionate, ethyl lactate, ethyl 2,3-dihydroxypropionate, ethyl pyruvate, ethyl acrylate, diethyl malonate, diethyl hydroxymalonate, n-propyl formate, n-propyl acetate, n-propyl glycolate, n-propyl glyoxylate, di-n-propyl oxalate, n-propyl propionate, n-propyl lactate, n-propyl 2,3-dihydroxypropionate, n-propyl pyruvate, n-propyl acrylate, di-n-propyl malonate, di-n-propyl hydroxymalonate, isopropyl formate, isopropyl acetate, isopropyl glycolate, isopropyl glyoxylate, diisopropyl oxalate, isopropyl propionate, isopropyl lactate, isopropyl 2,3-dihydroxypropionate, isopropyl pyruvate, isopropyl acrylate, diisopropyl malonate, diisopropyl hydroxymalonate, allyl formate, allyl acetate, allyl glycolate, allyl glyoxylate, diallyl oxalate, allyl propionate, allyl lactate, allyl 2,3-dihydroxypropionate, allyl pyruvate, allyl acrylate, diallyl malonate, diallyl hydroxymalonate, glycerol formal, 4-(hydroxymethyl)-1,3-dioxolan-2-one, 4-methyl-1,3-dioxolane, (2,2-dimethyl-1,3-dioxolan-4-yl)methanol, 1,4-dioxaspiro[4.5]decane-2-methanol, glyceraldehyde, 2,2-dimethyl-1,3-dioxolane-4-carbaldehyde, 1,4-dioxaspiro[4.5]decane-2-carbaldehyde, glycidol, glycidyl methyl ether, glycidyl ethyl ether, glycidyl n-propyl ether, glycidyl isopropyl ether, glycidyl n-butyl ether, glycidyl isobutyl ether, glycidyl sec-butyl ether, glycidyl tert-butyl ether, glycidyl allyl ether, glycidyl propargyl ether, glycidyl hexadecyl ether, glycidyl octyl/decyl ether, glycidyl phenyl ether, glycidyl benzyl ether, glycidyl formate, glycidyl acetate, glycidyl propionate, glycidyl isopropionate, glycidyl n-butyrate, glycidyl isobutyrate, glycidyl sec-butyrate, glycidyl acrylate, glycidyl methacrylate, diglycidyl 1,2-cyclohexanedicarboxylate, glycidyl benzoate, glycidyl 4-nitrobenzoate, epichlorohydrin, epibromohydrin, ribitol, arabitol, xylitol, mannitol, sorbitol, galactitol, allitol, iditol, and bis-(2,2-dimethyl-(1,3)dioxolan-4-yl methanol. This production of biobased chemicals 50 as described herein can allow for both the utilization of a renewable, carbonaceous by-product in the production of value-added chemicals and biobased products and an even greener biodiesel production 60 process.
Having thus described the invention, it is now claimed:
This application is a continuation-in-part and claims priority from U.S. Ser. No. 13/271,925, titled METHOD OF B10BASED CHEMICAL PRODUCTION FROM CRUDE BIOGLYCERIN, filed Oct. 12, 2011, which is incorporated herein by reference.
Number | Date | Country | |
---|---|---|---|
Parent | 13271925 | Oct 2011 | US |
Child | 13348794 | US |