MX2010007402A

MX2010007402A - System and method for refining carbonaceous material.

Info

Publication number: MX2010007402A
Application number: MX2010007402A
Authority: MX
Inventors: Randall J Harris; Damian Wales
Original assignee: Carbonxt Group Ltd
Priority date: 2008-01-08
Filing date: 2009-01-08
Publication date: 2010-12-21
Also published as: CN102159688A; WO2009089351A1; EP2231837A1; CA2711647A1; US20090172998A1; AU2009204100B2; JP2011509236A; AU2009204100A1

Abstract

A system for refining carbonaceous material including a carbonaceous material feedstock unit including a first vibratory screen unit for sizing the carbonaceous material; a digestion unit including a digestion unit in communication with the carbonaceous material feedstock unit; and an acid feedstock unit in communication with the digestion unit for providing an acid mixture solution to the digestion unit including a source of H2O; a source of HF; a source of H2SiF6, wherein the these compounds may be mixed together in ratios prior to being provided to the digestion unit; a separation unit in communication with the digestion unit for separating the digested carbonaceous material from the acid mixture solution; and a dryer unit in communication with the separation unit for drying the digested carbonaceous material and separating the carbonaceous material based on density.

Description

SYSTEM AND METHOD FOR THE REFINING OF MATERIAL CARBONÁCEO Field of the Invention The present invention relates to the carbonaceous material and more specifically to retinal carbon and carbon-related materials.

Background of the Invention Coal includes many organic and inorganic impurities in its natural condition, and these impurities create challenges to processes that use coal. For example, coal is used primarily as a fuel to produce electricity and heat through combustion. However, coal burning can be more problematic than ever due to growing pressure by environmental regulators on the owners / operators of facilities to reduce pollution. The retrofitting of coal-fired power plants with the latest polluting gas scrubbers is extremely costly.

In addition, coal can be used for a multitude of products from basic products to consumer products. For example, carbon can be used to make carbon blacks, inks, activated carbon, tar and the like. However, due to its composition, it includes large numbers of micropores and macropores that can contain many impurities, which makes it difficult to remove impurities during the processing of these products. Generally, it is beneficial to treat natural carbon to remove many of these impurities before using coal in these different applications.

Processes that treat coal to reduce impurities are known, which we normally refer to as the ash content. For example, it is known to use HF acid to remove contaminants from coal. A problem with using only HF acid by itself is that it is a highly reactive compound, and therefore reacts with essentially all contaminants. If the coal contains contaminants of calcium and magnesium species, then the HF acid produces CaF2 and insoluble gF2, which are not easily removed. Also some metal oxide contaminants are converted to metal fluorides, which may not be soluble in the HF acid. Additionally, substantial amounts of HF acid are used in these digests which is a costly component of the process.

In another example, U.S. Patent No. 4,780,112 describes the treatment of carbon with an acid of fluorine acid solution consisting of an aqueous solution of hydrofluorosilic acid (H2SiF4) and a hydrogen fluoride or hydrofluoric acid (HF). The available metal oxides are converted into metal fluorides and / or metal fluorosilicates, which are dissolved in the aqueous solution and then separated from the carbon. The treated coal is then washed with H2SiF4 to remove the metal fluorides from the surface of the treated coal and dried at a temperature between 70 ° C and 140 ° C. The dried coal is then heated to a temperature between 250 ° C and 400 ° C to remove H2SiF4 in the form of HF and SiF4.

In another example, US Patent No. 4,804,390 describes the treatment of the coal with HF and then the washing of the coal with H20 to leach the impurities. This is followed by a second leaching step that includes the treatment of the coal with a solution of hydrochloric acid, which is followed by another water wash. After each of these leaching steps, the acid solution is separated from the treated coal. Then the coal is heated to a temperature between 20 ° C and 100 ° C under vacuum to remove any residual HCL, HF and SiF4.

In still another example, US Patent Application Publication No. 20060150474 describes the treatment of the carbonaceous material with an aqueous solution of H2SiF6 in the absence of HF wherein the sulfur-containing impurities react with the H2SiF6 to form the digestion products and then Separate the digestion products from the treated carbonaceous material.

Brief Description of the Invention In one embodiment, the present system and method for refining the carbonaceous material ("system for refining carbonaceous material") provides improved digestion and decreased costs for said refining processes. The present system for refining carbonaceous material includes a carbonaceous material supply unit which acquires the raw carbonaceous material such as coal from a source that has been generally mechanically derailed. For example, the system for refining the carbonaceous material can take a stream from a settlement pond of a preparation plant containing small carbon particles of 0 to 5 mm in size and efficiently produce carbonaceous material having a desirable size and content. of water without requiring the expensive addition of the wetting steps found in the prior art. The carbonaceous material supply unit processes the carbonaceous material to a diameter preferably less than 1 mm in a wet strainer that washes and sizes the material. It can then be fed to a gravity separation unit that mechanically separates the carbonaceous material from the heavy impurities or the carbonaceous material exceeding the desired threshold. The separated impurities are deposited in a hopper to remove them and further processing or disposal while the washed carbonaceous material leaves the separation unit by gravity and is deposited in a vibrating dry sieve to reduce the remaining water content of the dimensioned carbonaceous material and washed to a desired level for use in a later digestion unit. The washed carbonaceous material can be sent to an additional drying process, using, for example, a microwave dryer to produce the carbonaceous material of a desirable moisture content. The carbonaceous material supply unit may further include the ultrasonic stimulus for the improved sizing and wetting of the carbonaceous material. In addition, the partially dewatered carbonaceous material can then be sent to a centrifuge to further reduce the water content of the carbonaceous material to a desired level for use in the subsequent digestion unit. The present system for refining the carbonaceous material may further include a moisture balancing apparatus that can increase the moisture content of the washed and sized carbonaceous material.

The current system for refining carbonaceous material also includes a digestion unit that uses inexpensive mixtures of fluorine-containing acids for digestion and removal of contaminants from the carbonaceous material. The system for refining the carbonaceous material includes adding the carbonaceous material of the carbonaceous material supply unit into a digestion unit containing at least one digestion vessel containing a mixture solution of H2SiF4 acids and HF acids and H20 The digestion vessel may include a mechanical agitator apparatus for completely mixing the carbonaceous material with the acid mixture solution. The production of the digestion vessel includes at least one paste of a digested or chemically treated carbonaceous material. Generally, there is sufficient physical separation of the carbonaceous material within the digestion vessel to produce different layers of treated carbonaceous material. In one aspect, these different layers of the carbonaceous material can be produced as different pastes from the digestion vessel in different descending vessels. The digestion unit may further include the ultrasonic stimulation of the carbonaceous material during the digestion step in a vessel at a frequency that creates cavitations with diameters approximately equal to or smaller than those of the micropores of the carbonaceous material, thereby creating an action of pumping or hydraulic as the bubbles collapse inside the micropores of the carbonaceous material. This action causes the acid mixture solution at elevated temperatures within the micropores and macropores allowing them to come into physical contact with the inorganic compounds contained therein., therefore facilitating in an important way the digestion. These sources of ultrasonic stimulation can include novel square-wave signals that generate the ultrasonic waves that create the desired sizes of cavitation bubbles. This ultrasonic action can provide up to 100% digestion of the contaminants contained in the carbonaceous material for use in ultra-clean fuel operations and for commercially viable processes to produce said clean carbonaceous material. In addition, the current system for retinating carbonaceous material can reduce digestion time, which increases productivity and improves economic viability. The system for the refining of the carbonaceous material further separates the carbonaceous material digested chemically from the acid mixture solution and the liquid waste products by means of, for example, a centrifuge. The carbonaceous material digested chemically can be washed with hot water, which can be followed by a vapor release process while in the centrifuge to remove as much of the solution from the acid mixture as possible and the liquid waste products from the carbonaceous material chemically treated and to reduce the moisture content of the carbonaceous material. The solution of the acid and the liquid waste products in tubing for the recycling tanks to filter the waste products, reuse them and reload the H2SiF6, which is then used again in this process. The dewatered chemically digested carbonaceous material exiting the centrifuge has a moisture content of preferably between 5% and 15%, and more preferably between 5% and 10% and can optionally be further dried at a moderate temperature (<130 ° C) in a dryer to reduce the moisture content without removing all the volatile components of the carbonaceous material.

The system for the refining of the carbonaceous material provides a novel process for the treatment of acid digestion and a subsequent mechanical separation of the treated coal from the pulp to remove metal impurities. The current system for refining the carbonaceous material does not pressurize the digestion vessel, thus saving energy consumption in the process. In addition, the current system for refining the carbonaceous material does not wash or rinse the structure of the carbonaceous material digested with H2SiF6 acid.

In one embodiment, the present system for refining the carbonaceous material produces refined carbon that is activated more rapidly to produce activated carbon. In addition, the quality of the activated carbons was produced in less time than it takes to manufacture similar activated carbons from the processes currently known. Additionally, the carbonaceous material produced with the present system to refine the carbonaceous material may allow conventional power plants to meet the emission requirements of the Environmental Protection Agencies of the United States of America without the current post-combustion treatment. Also, when the particle sizes of the carbonaceous material are below 10 microns, the burn time is between 0.05 seconds. The carbonaceous material with said characteristics produced by the present system for the refining of the carbonaceous material functions as the characteristics of oil and approaches the characteristics of natural gas when it is processed approximately 1 miera. With smaller combustion times experienced with the digested and dimensioned carbonaceous material, the residence time can be still less than 0.05 seconds, the combustion temperatures in a plant can be more easily controlled.

In one embodiment, the present system for refining the carbonaceous material may include a carbonaceous material supply unit that includes a first vibratory strainer unit for sizing the carbonaceous material; a digestion unit including a first digestion unit in communication with the carbonaceous material supply unit; a second digestion unit in communication with the first digestion unit; and an acid supply unit in communication with the digestion unit to provide an acid mixing solution for the first digestion unit including a source of H20; a source of HF; a source of H2SF6, wherein these compounds can be mixed together in proportions before being provided to the first digestion unit; a separation unit in communication with the digestion unit for separating the digested carbonaceous material from said acid mixture solution; and a cycling unit in communication with the separation unit for drying the digested carbonaceous material and separating the carbonaceous material based on the density.

The other embodiment, the current system for refining the carbonaceous material may include a carbonaceous material supply unit that includes a first vibratory strainer unit for sizing the carbonaceous material; a digestion unit including a digestion unit in communication with the carbonaceous material supply unit; and an acid supply unit in communication with the digestion unit to produce an acid mixing solution to the first digestion unit including a source of H20; a source of HF; a source of H2SiF6, wherein these compounds can be mixed together in proportions before being provided to the digestion unit; a separation unit in communication with the digestion unit to separate the digested carbonaceous material from the solution of the acid mixture; and a drying unit in communication with the separation unit for drying the digested carbonaceous material.

Brief Description of the Drawings Figure 1 illustrates a schematic diagram of a carbonaceous material supply unit according to an embodiment of the present invention: Figure 2 illustrates a schematic diagram of a microwave drying unit according to an embodiment of the present invention; Figure 3 illustrates a schematic diagram of a digestion unit according to an embodiment of the present invention; Figure 4 illustrates a schematic diagram of a fluidized milk dryer unit according to an embodiment of the present invention; Figure 5 illustrates a schematic diagram of a packaging and product unit according to an embodiment of the present invention; Figure 6 illustrates a schematic diagram of a vapor recovery unit according to an embodiment of the present invention; Figure 7 illustrates a schematic diagram of a supply storage unit according to an embodiment of the present invention; Figure 8 illustrates a schematic diagram of an ultrasonic unit according to an embodiment of the present invention; Figure 9 illustrates a schematic diagram of an ultrasonic unit according to another embodiment of the present invention; Y Figure 10 illustrates a flow chart of an example process for refining the carbonaceous material according to an embodiment of the present invention.

Detailed description of the invention In the drawings, the same or similar elements are designated with identical reference numbers in all the different views and figures thereof, and several illustrated elements may not necessarily be drawn to scale.

The term "carbonaceous" means all materials that consist of substantial amounts of carbon. No limitation of the term includes coal, refined coal, activated carbon, carbon black, coal products, solid crude oil, tar resin, carbon fibers, tar, coal, coke, graphite, and other carbon structures.

The term "digested carbonaceous material" means a carbonaceous material that has been subjected to cleaning or digestion processes as described herein. In one aspect, the term means the chemical cleaning of the carbonaceous material by digesting the minerals embedded within the carbonaceous material. This term can also mean a carbonaceous material that has been chemically cleaned and can be indicated as "chemically cleaned carbonaceous material".

The term "macropore" generally means pores having a diameter size greater than 50 nm. The term "micropore" generally means pores having a diameter size of less than 50 nm. The term "product" means all materials that are made from the refined carbonaceous material, including without limitation: plastics, fibers, solvents, pharmaceuticals, carbon black, inks, activated carbon, coal, tar, specialty minerals, boiler fuels , additives, gas cleaning - and the like.

Figure 1 illustrates a mode 100 of a carbonaceous material supply unit according to the present invention. In one embodiment, the carbonaceous material supply production unit 100 can be portable to be relocated to any location that produces a waste stream and / or a stream from a settling tank containing the carbonaceous material, such as the preparation of plants or laundries as is known to those skilled in the art. Generally, a preparation plant is a plant that washes, classifies, sizes, cleans, and the like a source of the carbonaceous material generally in the vicinity of the mining operation of the carbonaceous material, for example. Generally, these preparation plants produce carbonaceous material of similar sizes that are not further processed due to the cost of removing them from the carrier fluid stream, such as water. These carbonaceous particles of small size required can be produced from the washing of clays, carbonaceous material, and larger sized carbon rocks, which are generally separated and discarded using various processes related to the density in a preparation plant. They are generally discarded due to the size of the carbonaceous waste material too small or not worth the cost of recovering it from the process stream of the preparation plant, therefore this carbonaceous waste material flows with the waste water to the tanks of settlement where the carbonaceous material of waste sits on the bottom of the settlement tank, and the waste water is treated afterwards. In some cases, the percentage of the carbonaceous material in these settlement tank streams and / or settlement tanks may be between 25% and 75% of the total settlement tank depending on the age of the settlement tank. In one aspect, the system for refining the carbonaceous material can recover the carbonaceous material from a process stream of the preparation plant, such as a stream from the settlement tank. In another aspect, the system for refining the carbonaceous material can recover the carbonaceous material from a dam, such as a settlement tank.

The carbonaceous material supply production unit 100 can be moved or located near a carbonaceous material laundry, the carbonaceous material processing plant, the coal preparation plant, the coal mining plant, the embalming of the settlement, the embalming tank and the like where it is connected by means of the tube 102 to the waste stream of a preparation plant or the material of the settlement tank stream with added water containing carbonaceous material of smaller size. The tube 102 is connected to a vibrating strainer unit 104 that separates the largest carbonaceous material pieces from the smaller size pieces of the carbonaceous material. In one aspect, the vibrating strainer unit 104 includes a series of descending strainers to decrease the size of the selection. The vibratory strainer units 104 may include gravity and / or density separation apparatuses, such as rolling beds, straw tables, insoles, pulsating water beds, stable flow beds, and the like. Therefore, the larger sized pieces of carbonaceous material are selected in the upper strainers while the smaller size carbonaceous material falls through the lower parts of the vibratory strainer unit 104. In one aspect, one of the Intermediate strainers can contain the desired size of the carbonaceous material. In the processes on the outside, the water is supplied through the tube 106 to the unit of the vibrating strainer 104 for the improved washing and the processing in the unit of the vibrating strainer 104.

In one embodiment, the smallest size particles and the largest sized particles exceeding a previously determined desirable size of the carbonaceous material are removed from the vibrating strainer unit 104 by means of the tubes 108 and 110 and can be returned, by example, to the preparation plant. In the off-site process the water may also accompany undesirable particles coming out of the vibrating strainer unit 104. For ease of use, the tubes 102, 106, 108 and 110 may be flexible hoses, tubes and the like for easy connection from the production unit supplying the carbonaceous material 100 to the preparation plant. Particles of the desired size leave the vibrating strainer unit 104 and flow through the tube 112 to a density differential separator 114. In one embodiment, the density differential separator 114 separates the particles with the highest density from the particles. with lower density. Generally, the lower density particles will contain particles of the desired carbonaceous material that will be processed as will be described later. The higher density particles generally contain the material and particles that may not be used by the system for the refining of the carbonaceous material.

Particles of the desired size leave the density differential separator 114 and flow through the tube 122 to another vibratory strainer unit 120. In one aspect, the vibratory strainer unit 120 can further wash the particles and further dry the particles of the particles. carbonaceous material entering the vibrating strainer unit 120. Any sized particles other than the desired size can leave the vibratory strainer unit 120 via the tube 122 and be returned, for example, to the preparation plant. The washed and sized carbonaceous material can be further dried by forced air from a dryer 124. In one embodiment, the water content is preferably from about 8% to about 40% w / w, and more preferably from about 12% to approximately 18% p / p. As described more fully below, the carbonaceous material having said water content may be ideal for subsequent digestion processes and may eliminate the need and expense of re-moistening the dried carbonaceous material. This can also save energy that would otherwise be wasted to completely wet the dry carbonaceous material that is generally supplied to the refining plants. In one aspect, the water content can be further reduced in a preparation plant by the use of a microwave dryer and / or centrifuge unit to decrease the cost of transporting the carbonaceous material to an off-site refining plant. In this aspect, the water content of the carbonaceous material may be about 7% w / w.

Once the carbonaceous material possesses water at the desired levels, it can be transported by a conveyor or other appropriate apparatus to a high height to be placed inside the storage sacks, containers, tanks, trucks, containers, and the like (containers of storage 128). As described above, because the supply production unit of the carbonaceous material 100 can be movable or portable, the units described above can be mounted on a vehicle, such as a trailer 130. This makes it possible for the production unit supply of the carbonaceous material 100 is moved from one preparation site or plant to another to supply the last processes described herein with the carbonaceous material of a desired size and the water or moisture content, while reducing the waste stream flowing from , for example, the settlement tanks. In a modality, once the storage containers 128 are full, they can be loaded or moved to another vehicle (not shown) and can be transported to a microwave dryer unit or a digestion unit which will be fully described later. In one embodiment, the carbonaceous material supply production unit 100 may further include a centrifugal unit 132 for accepting a feed of the carbonaceous material from a vibrating strainer unit 120 to further reduce the moisture and / or water content of the carbonaceous material.

Figure 2 illustrates a mode 200 of a microwave dryer unit according to the present invention. In one embodiment, the system for refining the carbonaceous material includes a microwave drying unit 200 and in another embodiment the system for refining the carbonaceous material does not include a microwave drying unit 200. In this embodiment, the storage containers 202 and 128 are emptied into a hopper 204 which feeds a conveyor 206 which passes through the microwave unit 208 to provide additional decrease in water content of the carbonaceous material if this is desired. After leaving the microwave unit 208, the carbonaceous material can be transported by means of the conveyor 212 to a hopper 214 to feed it to the next unit of the process. The hoppers 204 and 214 can be vibrating hoppers to remove the carbonaceous material accumulated in lumps. In one embodiment, the microwave dryer unit 200 may further include a centrifugal unit 216 for accepting a feed of the carbonaceous material from the microwave unit 208 to further reduce the water and / or moisture content of the carbonaceous material. In another embodiment, the additional centrifuge units can be used with the microwave unit 208, so that, for example, they lie just before the microwave unit 208.

Figure 3 illustrates a mode 300 of a digestion unit according to the present invention. The digestion unit 300 may include a conveyor 302 for transporting the cleaned and dimensioned carbonaceous material to the humidity balance unit 346. The humidity balance unit 346 may include a source of water and steam that controllably increases the content of the water. moisture of the carbonaceous material clean and dimensioned. In cases where the moisture content of the carbonaceous material is reduced for transport purposes, then the moisture balance unit 346 can add moisture to the carbonaceous material. In one example, the moisture balance unit 346 can produce carbonaceous material with a moisture content of preferably from about 7% to about 40% w / w, and more preferably a moisture content from about 25% to about 35% p / p. After the moisture content in the moisture balance unit 346 has been adjusted or balanced, it can be fed to a conveyor 302, which transports the carbonaceous material to one or more digestion vessels 304, 308 and 310.

In one aspect, at the base of the conveyor 302 is a load cell 316 for weighing the carbonaceous material entering the conveyor 302. The digestion unit 300 includes an acid mixture solution that is conveyed from an H2SiF6 712 adjustment tank. (figure 7) by means of tube 318. The acid mixture solution is fed into the digestion vessel 304, which includes a mixer 312 and a heater 314. The carbonaceous material is fed into the digestion vessel 304 and the digestion of the carbonaceous material is initiated. A valve 306 can be used to change the solution of the carbonaceous material / acid mixture between the digestion vessels 304, 308 and 310. In one aspect, the digestion vessels 304, 308 and 310 can be fed by gravity to one another or pumped by the pumps described here.

The carbonaceous material and the acid mixture solution can then be fed into one of the digestion vessels 308 and 310 where the carbonaceous material is further digested. Digestion vessels 308 and 310 also include heaters 324 and 326, respectively, and mixers 322 and 326, respectively. The heaters 314, 324 and 326 are used to maintain the digestion temperature of the carbonaceous material in the digestion vessels 304, 308 and 310. The heaters can be steam-heated heat exchangers as is generally known in the art.

By having lower digestion vessels 308 and 310, the carbonaceous material / acid solution mixture can be further digested while a new batch is being loaded into the digestion vessel 304. Additionally, the carbonaceous material / acid solution mixture is not found within the specifications, can be discharged into one of the digestion vessels 308 and 310 for further treatment without stopping digestion in the digestion vessel 304. In addition, the carbonaceous material / acid mixture solution can then be moved or pumped into the vessel of digestion 310, which can be used for further digestion of the carbonaceous material / acid mixture solution or can be used as a container, a stage or a reservoir container for feeding a centrifuge 328 by means of tube 330 , which may have a capacity or volume that is less than that of digested containers 304, 308 and 310.

In one embodiment, the digestion vessels 304, 308 and 310 further include condensation circuits 348 which can take any acid mixture solution that is vaporized in the digestion vessels 304, 308 and 310. The condensation circuits 348 may include condensing units, such as chillers, to condense the steam or the gaseous acid mixture solution to store it in the current system to retinal the carbonaceous material. The separators, generally known in the art, can be additionally used to separate the different components or compounds of the solution from the acid mixture. In another embodiment, the catalyst beds can be used with the condensation circuits 348. In one aspect, the acid mixing solution can contain multiple acid compounds such as HF and H2SiF6, which can be separated from each other by the use of temperature-controlled separators that separate the different compounds by specific temperature distillation. This separation can be controlled by controlling the temperature and the proportion of acidic compounds within the separators. In addition, metals deposited outside the carbonaceous material can be precipitated at different pH levels and then filtered from the carbonaceous material / acid mixture solution.

In the embodiments described above, the current system for refining the carbonaceous material can include multiple digestion vessels that are in series, one feeding the solution of the acid / carbonaceous material mixture to another lower digestion vessel. In this embodiment, the carbonaceous material / acid mixture solution can be produced in batches in a manner having a continuous downward flow, which can be important for continuous feeding to centrifuge 328, for example, by means of tube 330 .

In another embodiment, the present system for refining the carbonaceous material may include a digestion vessel by itself, such as the digestion vessel 304. In this embodiment, no further descending digestion vessels of the carbonaceous material / acid mixture solution are fed. and is fed directly, for example, to a centrifuge 328.

In yet another embodiment, the present system for refining the carbonaceous material may include multiple digestion vessels that are in parallel feeding consecutively or simultaneously the carbonaceous material / acid mixing solution, for example, to the centrifuge 328. In this embodiment , the digestion vessels 304, 308 and 310 are each individually fed with the carbonaceous material / acid mixture solution of the conveyor 302.

Preferably, the acid mixture solution comprises HF and H2SiF6 in a range of proportions. In one example, the HF is preferably present in a range from about 2% to about 20% w / w, and more preferably from about 5% to about 15% w / w. The H2S.F6 is present in a range of preferably from about 10% to about 58% w / w. Preferably, the HF is present in a range from about 5% to about 12% w / w, and more preferably in a range from about 8% to about 10% w / w and H2SiF6 is present in a range preferably from about 30% to about 38% w / w, and more preferably from about 22% to about 32% w / w. The rest of the mixture is water. Therefore, for example, in one aspect, an acid mixture solution that includes 10% HF and 35% H2SiF6 will have an H20 content of 55% taking into account the moisture of the carbonaceous material being fed. to the digestion vessels. Preferably, the solution of the acid mixture includes these mixed portions of HF and H2SiF6 before mixing them with the carbonaceous material.

In another embodiment, a fluorine acid solution can be prepared from a solution of H2SiF6 plus H20 as the basic acid to which the anhydrous HF acid is added so that both of these reactive acids are in a solution. Some exemplary ranges of the acids are from about 5% to 34% w / w H2SiF6, from 32% to 90% w / w H20, and from 5% to 34% w / w HF acid. In one aspect, a fluorine solution of a saturated solution of H2SiF6 in water is prepared by adding the anhydrous gas HF acid. In another embodiment, SiF4 can be reacted with H20 to form H2SiF6.

In one embodiment, the digestion vessels 304, 308 and 310 can be operated at temperatures from about 10 ° C to about 125 ° C and at a pressure of about 0 kPa (0 kg / cm2) to about 105 kPa (1.07 kg / cm2) ). In another embodiment, the temperature of the digestion vessels 304, 308 and 310 may preferably be in the range of about 55 ° C to about 85 ° C, and more preferably in the range of about 70 ° C to about 85 ° C.

In one embodiment, the carbonaceous material / acid mixture solution is stirred in the digestion vessels 304, 308 and 310 preferably from about 20 to about 80 minutes, and more preferably from about 40 to about 60 minutes.

The digestion vessels 304, 308 and 310 can be made of a material that resists the chemicals contained therein. For example, the digestion vessel 304 may be made of a mixture of plastic and carbon fiber composites or any structural material coated with any material that is impervious to the corrosive effects of the acid used.

The carbonaceous material treated has a specific gravity lower than the carbonaceous material / acid mixture solution, therefore the carbonaceous material may float towards the top of the carbonaceous material / the acid mixture solution in the digestion vessels 304, 308 and 310 when the mixers 312, 322 and 324 are turned off. Non-reactivated iron sulfide and other undissolved heavy metal salts whose specific gravities are greater than those of the acid mixture solution may fall to the bottom of the digestion vessels 304, 308 and 310 if the agitation is stopped by turning off the mixers 312, 322 and 324. In one embodiment, the specific gravity of a certain carbonaceous material such as carbon is about 1.3 and that of the acid mixture solution is about 1.2 when it enters the digestion vessel. After digestion, the carbonaceous material then generally has a specific gravity of 1.1 and the specific gravity of the acid solution is 1.2 which enters the centrifuge 328. Furthermore, during the separation process, the treated carbonaceous material acts as a filter for the metal chlorides and / or metal fluorosilicates that are contained in the acid mixture solution.

In one embodiment, the tube 330 is connected to a pump 332 that pumps the carbonaceous material / acid mixing solution to the centrifuge 328. Preferably, the pump 332 pumps the carbonaceous material / acid mixing solution without degrading the size of particle. In one aspect, the pump 332 is a peristaltic pump.

In one aspect, the centrifuge 328 may include several different stages. For example, it can rotate at a sufficient speed to remove the acid mixture solution from the carbonaceous material in a first stage. In a second step, the water supplied from a supply of deionized water 336 and / or a supply of water for rinsing 334 can be used in the washing of the carbonaceous material. Preferably, this rinse water can be applied to the carbonaceous material while it is being agitated inside the centrifuge 328. The water used in this cycle can be heated before it is admitted to the centrifuge 328. For example, the water may be at a temperature preferably from about 30 ° C to about 100 ° C and more preferably from 75 ° C to about 85 ° C. Then, the centrifuge 328 can remove this wash water where it can be recycled after being filtered through a filtration apparatus in this second stage. The rinse water that is removed from the centrifuge 328 is sent for recycling by means of the tube 342 as described below. In another embodiment, the wash water removed from the centrifuge 328 can be sprayed into the carbonaceous material before it enters the digestion vessels 304, 308 and 310 in the humidity balance unit 346 as the moisture content of the carbonaceous material incoming which is lower than desired before digestion as described herein. The filter apparatus removes some of the metal fluorides and metal chlorides which can be sold to other markets, such as aluminum and steel plants.

Preferably, the third step includes injecting steam into the centrifuge 328 during the agitation process. In one embodiment, the temperature within the centrifuge 328 is preferably from about 120 ° C to about 400 ° C, and the amount of steam that is applied to the carbonaceous material in the centrifuge 328 can be determined by several factors, including the size of the the particles of the carbonaceous material and the speed of the drum inside the centrifuge 328 to prevent the carbonaceous material from accumulating inside the centrifuge 328. The vapor helps to remove the residual fluorides. For example, the amount of steam applied to the carbonaceous material can be determined by the residual level of fluorine required in the finished carbonaceous material. For example, an isotropic HF, H2SiF6 and H20 can vaporize preferably from about 105 ° C to about 120 ° C depending on the concentrations of the individual compounds. Therefore, providing steam to centrifugal 328 of HF, H2SF6 and residual H20 is discarded from the carbonaceous material as a vapor and then recovered by means of tube 342, for example, the steam process can also start from the drying of the current system to refine the carbonaceous material.

The centrifuge 328 may further include discarders that remove the carbonaceous material from the centrifuge 328, discarding the carbonaceous material as it is inside the centrifuge 328. Therefore, the carbonaceous material leaves the centrifuge 328; and then the carbonaceous material is moved to a hopper 344 by means of the conveyor. In one aspect, it may be important not to use transportation means that degrade the carbonaceous material to avoid the creation of smaller, undesirable wastes. The moisture content of the carbonaceous material at this point can be from about 4% to about 12% w / w.

Figure 4 illustrates a mode 400 of a drying unit according to the present invention. The drying unit 400 includes a dryer 402 which can further dry the carbonaceous material produced in the digestion unit 300. The carbonaceous material of the hopper 344 is fed into the dryer 402 where the carbonaceous material is subjected to the air flow of a desired speed and temperature. After a residence time of the carbonaceous material leaving the dryer 402 and is fed to a hopper 406 where it can be raised above the packing unit and final product 500 which can include a load cell or scale 504 for weighing the material carbonaceous finish which is placed in the storage container 502 as shown in figure 5, or sent to the bulk storage where the almost pure and dry carbonaceous material is ready for the next stage, fuel, activation or the like.

In one embodiment, the dryer 402 may be a fluidized bed that is generally a density dependent unit, such as a roll bed having an air flowing from the bottom to the top of the fluidized bed dryer that pulls the carbonaceous material lighter off the top of the fluidized bed dryer to transfer it to the drum 410 of a centrifuge 408. The particles of the carbonaceous material are suspended in the air flow based on their density and further dried by this process. Particles of the average size carbonaceous material that do not flow out of the top of the fluidized bed dryer are recovered at the bottom of the fluidized bed dryer to transfer them to the conveyor 404. The fluidized bed dryer includes a dam that controls the height of the carbonaceous material inside the fluidized bed dryer. The conveyor 404 may be a vacuum conveyor as is known in the art. In one aspect, particles of the smaller size carbonaceous material leaving the top of the fluidized bed dryer can be about 200 microns or less. To control the separation of particle sizes through the fluidized bed dryer, the air flow can be adjusted. A higher air flow through the fluidized bed dryer will produce particles of carbonaceous material of larger size that leave the top of the fluidized bed dryer while a lower air flow will produce particles of carbonaceous material of smaller size than come out of the top of the fluidized bed dryer. In addition, particles of carbonaceous material of smaller size can be fed into the storage container, such as sacks and the like.

In another embodiment, the dryer 402 may be a number of designs as long as there is an air flow and movement of the carbonaceous material, the temperature of the dryer 402 may preferably be in a range of about 100 ° C to about 160 ° C, more preferably from about 120 ° C to about 140 ° C, and the temperature may be high enough to remove most of the moisture and some of the tar in order to release the residual fluorine to a level close to the inherent value of the carbonaceous material original.

Figure 6 illustrates a mode 600 of a steam recovery unit 600 according to the present invention. The process water produced by the system for the refining of the carbonaceous material can be fed to a gas scrubber 602 wherein the air is extracted through the scrubber 602 to remove any additional light volatile vapors from the process water. The flow of air through the gas scrubber 602 is provided by the fans 608 which are fed to a stack 610. The water from the detached process can be returned to the top of the scrubber 602 by means of the pump 612. Additionally, the water from the detached process can be fed to the moisture balance unit 346 which is to be used as a supply to increase the moisture content of the carbonaceous material within the humidity balance unit 346.

Figure 7 illustrates a mode 700 of a supply storage unit according to the present invention. The supply storage unit 700 includes a deionized water storage tank 702 to maintain the deionized water that is used in the system to refine the carbonaceous material. For example, the deionized water is fed from the deionized water storage tank 702 to the centrifuge 328 via the tube 704. The supply storage unit 700 further includes a storage tank of HF 706 which feeds the HF acid by means of the tube 708 to an HF 710 adjusting tank, and an H2SiF6 712 adjusting tank may further include heaters for heating their respective acid mixing solutions after mixing the acid mixing solution at a desirable strength. The adjustment tank of H2SiF6712 can be further fed with H2SiF6 in a more concentrated form which is stored in a storage tank of H2SiF6 714. Once the desired strength of the acid mixing solution is achieved, then it is introduced into the tubes by means of the tube 716 for the digestion vessel 304 to mix the carbonaceous material. In addition, the HF 710 adjusting tank can feed a reduced force of HF to the centrifuge 328 via the tube 718. Also, the supply storage unit 700 can further include a rinse water collection tank 722 containing the rinse water collected from the system to refine the carbonaceous material. This rinse water can be fed to the centrifuge 328 by means of the tube 720. The additional containers 724 and 728 can be used to contain caustic compounds, such as bases, to neutralize any acid spills or reduce the acid strength of the system. to refine the carbonaceous material. Said bases can be fed to the digestion vessel 304 by means of the tube 726.

Figure 8 illustrates an embodiment 800 of an ultrasonic unit according to the present invention. In one embodiment, the digestion vessels 304, 308 and 310 may include a tube 802 that takes a stream of an acid / carbonaceous mixture solution and pumps it through the tube 802 through an ultrasonic wave source 804 to the improved penetration of the acid mixture solution into the micropores and macropores of the carbonaceous material. In one aspect, the ultrasonic wave source 804 may be a water bath that is subjected to a source of said ultrasonic waves, thereby imparting the ultrasonic waves through the tube 802 for improved penetration of the acid mixing solution. . In one embodiment, the wave signals are square to improve said penetration and digestion action.

Figure 9 illustrates an embodiment 900 of an ultrasonic unit in accordance with the present invention. In this embodiment, the ultrasonic wave source 902 is placed on the tube 102 before entering the vibrating strainer unit 104.

In one embodiment, the frequency of the ultrasonic wave source 804 and 902 is from about 80 KHz to about 100 KHz. In one example, an opening of a macropore of the carbonaceous material can be about 1 miera and it has been found that a frequency of a 100 KHz source of ultrasonic waves 804 and 902 will cause the acid mixture solution to penetrate into the opening of the macropore. Additionally, as the acid mixture solution is pumped into the macropores of the carbonaceous material, a pressure is created within the macropore causing the acid mixture solution to be pumped once the pressure becomes higher within the macropore than outside the macropore. The pumping action provides improved penetration and digestion of contaminants from the carbonaceous material. The ultrasonic wave source 804 and 902 can be generated by ultrasonic transducers that are well known in the art. In one aspect, these transducers may be in contact or communication with a water bath, which transfers the action of the wave to the water, which then transfers the action of the wave to the tube, and so on, to provide the action of pumping to the micropores and macropores of the carbonaceous material. This reduces the need for mechanical agitation which provides improved digestion times. The frequency of the ultrasonic wave source 804 and 902 causes cavitations, cavitation bubbles and / or cavity bubbles within the acid mixture solution so that they are small or smaller than the typical openings of the macropores of the carbonaceous material . In general, at a larger pressure, smaller cavitation bubbles. If the cavitation bubbles are too large, they may tend to pulverize the carbonaceous material into smaller sizes that may not be desirable for the process. In one embodiment, the ultrasonic wave source 804 and 902 have the ability to produce power from about 250 watts to about 16,000 watts with a frequency of about 10 KHz to about 50 KHz. Ultrasonication can be performed at an increased pressure over the ambient pressure using a feed pump and an adjustable counter-pressure valve next to the tube where you want to operate.

In addition to the above-mentioned aspects and embodiments of the present invention for retinating the carbonaceous material, the present invention further includes methods for retinating the carbonaceous material. Fig. 10 illustrates one embodiment 1000 of a method for refining carbonaceous material. In step 1002, the acid mixture solution is prepared by mixing HF, H20 and H2SiF6 acids at a desired ratio. In this step, the stored concentrated HF and H2SiF6 acids can be pumped individually to individual containers where the concentration of each is reduced with water or a base. Then, these reduced concentrations of the HF and H2SiF6 acids can be combined in a vessel which then mixes and heat the mixture of HF, H2SF6 and H20 acids. In this step, the exact amount of the acid mixture solution is prepared for a specific amount of the carbonaceous material to be digested.

In step 1004, the carbonaceous material is prepared by sizing a source of carbonaceous material, such as the stream from the settlement tank of the preparation plant. This step further includes wetting the carbonaceous material with H20 at a desired content, such as from about 8% to about 10% w / w. This step may further include application of ultrasonic waves to the carbonaceous material before or during the sizing operation.

In step 1006, the carbonaceous material and the acid mixture solution are combined in a digestion vessel which has a controlled temperature and pressure. This step may further include transferring the carbonaceous material / acid mixture solution to a second digestion vessel for the additional digestion time. This step may further include transferring the carbonaceous material / acid mixture solution to a third digestion vessel for addition at the time of digestion. This step may also include the application of ultrasonic waves to the digestion vessel or to a returned tube or circuit that takes a jet of the carbonaceous material / acid mixture solution out of the digestion vessel and then back into the vessel of digestion after the application of ultrasonic waves for improved digestion.

In step 1008, the carbonaceous material / acid mixture solution is transferred to a centrifuge for the removal of the acid mixture solution. This step may further include spraying rinsing water into the centrifuge to wash any residual acid mixture solution the carbonaceous material. This can be followed by further centrifugation until the carbonaceous material has a desirable moisture content.

In step 1010, the carbonaceous material can be further dried and separated based on the densities to achieve the desired product size for a particular application or order. This step may include applying an air flow in a vertical vessel so that the less dense carbonaceous material is removed from the top of the dryer while the denser carbonaceous material is retained in the dryer for removal to a storage vessel, such as a sack. In step 1012, the carbonaceous material is finished and weighed in the final storage containers, such as sacks for its intended purpose. The process described here is independent of the scale and can be used in a micro-scale, meso-scale and macro-scale.

A system for retinating carbonaceous material has been described. It should be understood that the particular embodiments described within this specification are for purposes of example and should not be construed as limiting the present invention. Furthermore, it is evident that those skilled in the art can now make numerous uses and modifications of the specific embodiments described without departing from the concepts of the invention. For example, different temperatures, pressures, compositions of the acid mixture solution can be changed or altered to fit within the present system for refining the carbonaceous material described herein or others without departing from the concepts of the present invention.

Claims

1. A system for refining carbonaceous material which comprises: a carbonaceous material supply unit comprising: a first vibratory strainer unit for sizing said carbonaceous material to a desired size; a density differential separation apparatus in communication with said vibrating strainer unit to produce a carbonaceous material with a mineral content of 5%; a digestion unit in communication with said carbonaceous material supply unit; an acid supply unit in communication with said digestion unit to provide an acid mixing solution to said first digestion unit comprising: a source of H20; a source of HF; a source of H2SiF6, wherein said HF, H2SiF6 and H20 can be mixed together in predetermined proportions to form said acid mixing solution before being provided to said first digestion unit; a separation unit in communication with said digestion unit for separating the digested carbonaceous material from the acid mixture solution; Y a drying unit in communication with the separation unit to dry the digested carbonaceous material and separate the carbonaceous material.

2. The system for the refining of carbonaceous material as described in claim 1, characterized in that said carbonaceous material supply unit comprises: a supply of the material from the settling tank stream of a carbonaceous material preparation plant and a settling tank of the carbonaceous material connected to said first vibratory material.

3. The system for the refining of carbonaceous material as described in claim 1, characterized in that the unit producing the supply of the carbonaceous material is a portable unit.

4. The system for the refining of carbonaceous material as described in claim 1, characterized in that said digestion unit further includes: a peristaltic pump located between the digestion unit and in the separation unit for pumping said carbonaceous material / acid mixture solution of said digestion unit to said separation unit with minimal degradation of the particles.

5. The system for the refining of carbonaceous material as described in claim 1, characterized in that said separation unit is a centrifuge.

6. The system for the refining of carbonaceous material as described in claim 1, characterized in that said separation unit further includes: A rinse of H20 to rinse any residual acid mixture solution of the digested carbonaceous material.

7. The system for the refining of carbonaceous material as described in claim 1, characterized in that said separation unit further includes: a steam rinse to rinse any residual acid mixture solution of the digested carbonaceous material.

8. The system for the refining of carbonaceous material as described in claim 1, characterized in that it also comprises: a unit dependent on the density of the fluidized bed in communication with the separation unit for drying said digested carbonaceous material, wherein the drying process separates the digested carbonaceous material based on the density of the digested carbonaceous material, and wherein the drying process and separation can be controlled by the speed of an air flow through the unit dependent on the density of the fluidized bed.

9. The system for the refining of carbonaceous material as described in claim 8, characterized in that it also comprises: a vacuum conveyor in communication with the unit dependent on the density of the fluidized bed to transport the dry digested carbonaceous material from said fluid dependent density unit to a finished product container of carbonaceous material.

10. The system for the refining of carbonaceous material as described in claim 1, characterized in that at least one of said unit of supply of the carbonaceous material and said digestion unit further comprise: an ultrasonic wave generator for producing ultrasonic waves of a size sufficient to cause cavitation bubbles having a diameter smaller than the average diameter of an opening of a macropore of said carbonaceous material.

11. A method to refine the carbonaceous material which comprises: provide a digestion unit; feeding an acid mixture solution consisting of a mixture of H20, HF, and H2SiF6 in said digestion unit, wherein said HF, H2SiF6, and H20 acids can be mixed together in predetermined proportions to form the mixed solution of acids before it is fed to the digestion unit; feeding a supply of carbonaceous material previously wetted in the digestion unit to form a carbonaceous material / acid mixture solution; digest said carbonaceous material to remove contaminants, where the contaminants are soluble in the acid mixture solution; pumping the carbonaceous material / acid mixture solution of the digestion unit to a separation unit; separating the digested carbonaceous material from the carbonaceous material / acid mixture solution; Y subjecting the carbonaceous material directed to a desired velocity of a hot air flow, wherein the desired velocity of the hot air flow separates the digested carbonaceous material based on the density of the carbonaceous material and wherein said desired velocity of the hot air flow is It also dries the digested carbonaceous material.

12. The method for refining the carbonaceous material as described in claim 11, characterized in that said feeding of a previously moistened carbonaceous material supply comprises: receiving a supply of carbonaceous material from one of a carbonaceous material preparation plant and a carbonaceous material settling tank stream.

13. The method for refining the carbonaceous material as described in claim 11, characterized in that the feed of the acid mixture solution further comprises: heating the solution to a temperature of about 55 ° C to about 85 ° C.

14. The method for refining the carbonaceous material as described in claim 11, characterized in that providing a first digestion unit further comprises: providing a second digestion unit in combination with the first digestion unit for transferring the carbonaceous material / acid mixture solution for further digestion.

15. The method for refining the carbonaceous material as described in claim 11, characterized in that the separation of the carbonaceous material from the carbonaceous material / acid mixture solution further comprises: removing the solution from the acid mixture of the carbonaceous material by subjecting the acid mixture solution to centrifugal forces.

16. The method for refining the carbonaceous material as described in claim 15, characterized in that removing the acid mixture solution further includes: Rinse the carbonaceous material with rinse water during centrifugal forces.

17. The method for refining the carbonaceous material as described in claim 15, characterized in that the removal of the solution from the acid mixture further includes: Rinse the carbonaceous material with steam during the centrifugal forces.

18. The method for refining the carbonaceous material as described in claim 11, characterized in that at least one of said feed supply of carbonaceous material previously moistened and the digestion of said carbonaceous material further comprises: subjecting the carbonaceous material to an ultrasonic wave of a size sufficient to cause cavitation bubbles having a diameter smaller than the average diameter of an opening of a macropore of the carbonaceous material.

19. A system for refining a carbonaceous material which comprises: means for providing a digestion unit; means for feeding an acid mixture solution consisting of a mixture of H20, HF, and H2SF6 into the digestion unit, wherein said HF, H2SiF6, and H20 acids can be mixed together in predetermined proportions to form said acid mixture solution before being fed into the first digestion unit; means for feeding a supply of carbonaceous material previously wetted in the first digestion unit to form a carbonaceous material / acid mixture solution; means to digest the carbonaceous material to eliminate contaminants, wherein the contaminants are soluble in the acid mixture solution; means for pumping the carbonaceous material / acid mixture solution of said digestion unit to a separation unit; means for separating the targeted carbonaceous material from the acid mixture solution; Y means for subjecting the carbonaceous material directed to a desired rate of hot air flow, wherein the desired velocity of the hot air flow separates the carbonaceous material directed based on the density of the carbonaceous material, and wherein the desired velocity of the air flow hot further dry the digested carbonaceous material.

20. The system for refining the carbonaceous material as described in claim 19, characterized in that said means for feeding a supply of previously moistened carbonaceous material comprises: means for receiving a supply of carbonaceous material from a jet from a settlement tank of the carbonaceous material preparation plant.

21. The system for refining the carbonaceous material as described in claim 19, characterized in that the means for feeding the acid mixture solution further comprise: means for heating the solution at a temperature of about 55 ° C to about 85 ° C.

22. The system for refining the carbonaceous material as described in claim 19, characterized in that the means for providing a digestion unit further comprise: means for providing a second digestion unit in communication with the digestion unit for transferring the carbonaceous material / acid mixture solution for further digestion.

23. The system for refining the carbonaceous material as described in claim 19, characterized in that the means for separating the carbonaceous material directed from the carbonaceous material / acid mixture solution further comprises: means for removing the acid mixture solution from the carbonaceous material by subjecting said acid mixture solution to centrifugal forces.

24. The system for refining the carbonaceous material as described in claim 23, characterized in that the means for removing the acid mixture solution also include: means for rinsing the carbonaceous material with steam during said centrifugal forces:

25. The system for refining the carbonaceous material as described in claim 19, characterized in that at least one of said means for feeding a supply of previously moistened carbonaceous material and means for digesting the carbonaceous material further comprises: means for subjecting the carbonaceous material to an ultrasonic wave of a size sufficient to cause cavitation bubbles having a diameter smaller than the average diameter of an opening of a macropore of the carbonaceous material.