PROCESS TO REMOVE AND RECOVER SULFUR DIOXIDE

专利摘要:
processes for removing and recovering sulfur dioxide and simultaneous sulfur dioxide removal process and nox are processes for the selective removal of contaminants from effluent gases. more particularly, some embodiments of the present invention relate to the selective removal and recovery of sulfur dioxide from effluent gases in a sulfur dioxide absorption/desorption process using an aqueous buffered absorption solution comprising certain organic acids or weak inorganics or salts thereof, preferably certain polyprotic carboxylic acids or salts thereof, to selectively absorb sulfur dioxide from the effluent gas. oxidation inhibitors can be used. the absorbed sulfur dioxide is subsequently extracted to regenerate the absorption solution and produce a gas enriched in sulfur dioxide content. absorption solution regeneration can include an integrated sulfur dioxide extractor and heat pump system to provide improved energy efficiency. other embodiments of the present invention relate to a process for simultaneous removal of sulfur dioxide and nitrogen oxides (nox) from effluent gases and recovery of sulfur dioxide. the process uses an aqueous buffered absorption solution that additionally includes a metal chelator to desorb sulfur dioxide and nox from the gas and subsequently reduce the absorbed nox to form nitrogen. further, the present invention provides a process for controlling the contaminating concentration of sulfate salt in the absorption solution by partial crystallization and removal of the sulfate salt crystals.
公开号:BR112013010219B1
申请号:R112013010219-5
申请日:2011-10-28
公开日:2021-06-01
发明作者:Ernesto Vera-Castaneda
申请人:Mecs, Inc；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] This invention relates to processes for the selective removal of contaminants from effluent gases. The present invention is particularly useful in producing a gas enriched with sulfur dioxide from effluent gases relatively low in sulfur dioxide content. BACKGROUND OF THE INVENTION
[002] Gaseous effluents containing sulfur dioxide are produced through a variety of operations, which include the roasting or smelting of sulphidic metal ores and concentrates and the combustion of carbon fuels containing sulfur (eg flue gases of coal-burning power stations). Carbon fuels play a significant role in electricity generation, providing heat energy and transport fuels. Most carbon fuels contain sulfur which, when burned, turns to sulfur dioxide. The sulfur dioxide emitted contributes to a wide range of environmental and health problems. As emerging economies expand, their energy demand increases rapidly and as lower carbon sulfur fuels are depleted, more oil and coal reserves that have progressively higher levels of sulfur will be utilized inducing higher dioxide emissions. of sulfur.
[003] There are also increasing regulatory pressures to reduce sulfur dioxide emissions worldwide. The most commonly used method to remove sulfur dioxide is through absorption or adsorption techniques. A common approach is the contact of sulfur dioxide with an aqueous stream that contains an accessible base. Sulfur dioxide dissolves in water to form sulfuric acid (H2SO3) which, in turn, reacts with the base to form a salt. Common bases are sodium hydroxide, sodium carbonate and lime (calcium hydroxide, Ca(OH)2). The pH starts at about 9 and is reduced to about 6 after reduction with sulfur dioxide. A one-stage wet scrubbing system typically removes up to 95% of sulfur dioxide. Wet scrubbers and similarly dry scrubbers require capital investment, variable costs due to lime consumption and solids disposal, and consume energy and services to operate such sulfur dioxide removal systems.
[004] Rather than reacting with a lime-like base, sulfur dioxide in effluent gases can be recovered to be marketed as a product or used as part of a feed gas to a contact sulfuric acid facility and recovered as sulfuric acid and/or oil to meet the growing global demand of the fertilizer industry or to produce refined sulfur dioxide. In addition to pointing out the environmental and health problems associated with sulfur dioxide emissions, this approach recovers sulfur values from coal and other carbon fuels. However, these gas streams often have relatively low sulfur dioxide concentration and high water vapor concentration. Where the concentration of sulfur dioxide in the gas fed to a sulfuric acid plant is less than about 4 to 5 percent by volume, problems can increase with respect to both the water balance and energy balance in the acid plant. More particularly, the material balance of a conventional sulfuric acid plant requires that the molar ratio of H2O/SO2 in the sulfur dioxide-containing gas stream fed to the plant is not greater than the molar ratio of H2O/SO2 in the acid. product. If the desired product acid concentration is 98.5 percent or above, that ratio cannot be more than about 1.08 in the sulfur dioxide containing gas stream fed to the facility. As generated, the effluent gases from metallurgical processes and flue gases from the combustion of sulfur fuels often have a water vapor content above the ratio of 1.08, which cannot be sufficiently reduced by cooling the gas without significant capital expenditures and gas. Furthermore, if the sulfur dioxide gas force of the effluent gas is below about 4 to 5 percent by volume, it may not be sufficient for autothermal operation of the catalytic converter. That is, the heat of conversion from sulfur dioxide to sulfur trioxide may not be large enough to heat the inlet gases to catalyze operating temperatures and, as a consequence, heat from some external sources must be supplied. This, in turn, also increases both operating costs and capital requirements for the sulfuric acid installation.
[005] The strength of sulfur dioxide from off-gases can be enhanced by selectively absorbing sulfur dioxide in a suitable solvent and subsequently depleting the absorbed sulfur dioxide to produce regenerated solvent and an enriched gas of sulfur dioxide content. A variety of aqueous solutions and organic solvents and solutions have been used in sulfur dioxide absorption/desorption processes. For example, aqueous solutions of alkali metals (eg sodium sulfite/bisulfite solution), amines (eg, alkanolamines, tetrahydroxyethylalkylenediamines, etc.), amine salts, and salts of various organic acids have been used as dioxide absorbers of regenerable sulfur.
[006] Buffer solutions are also effective in absorbing sulfur dioxide. Fung et al. (2000) provide data on sulfur dioxide solubility for a 1 molar solution of phosphoric acid and sodium carbonate at a ratio of about 1.57 Na/PO4 as a function of temperature. Data are for virgin mixture and mixture in which 1000 ppm adipic acid is added to enhance sulfur dioxide solubility. Fung et al. it also indicates that when taken at a boiling temperature, 95% and 65% of the sulfur dioxide is removed, respectively, into the virgin mixture and the mixture containing adipic acid. Calculations on solution pH show that the pH changes from 6 to about 3 as sulfur dioxide is absorbed. So with organic solvents there is a slight reaction of sulfur dioxide with oxygen, forming sulfur trioxide. Although this reaction is very limited and when Na2CO3 is used, it is further inhibited by its reaction with free radicals formed during oxidation, the sulfur trioxide that is formed induces the formation of sodium sulfate, which, if the Sodium sulfate is removed by crystallization, is removed as sodium sulfate decahydrate (Na2SO4-10H2O), also known as Glauber's Salt. This salt can be removed by taking a drag stream and cooling it to force precipitation of Glauber's Salt which is easily crystallized and removed by a screening, filtration, centrifugation or other solid/liquid separation technique.
[007] US patent application 4,133,650 (Gamerdonk et al.) discloses a regenerative process for recovering sulfur dioxide from exhaust gases with the use of a regenerable aqueous dicarboxylic acid (e.g., phthalic acid, maleic acid, malonic acid and glutaric acid and mixtures thereof) buffered wash solution at a pH of about 2.8 to 9. The recovered sulfur dioxide can be used in the production of sulfuric acid.
[008] Similarly, US patent application 2,031,802 (Tyrer) suggests using salts of substantially non-volatile acids that have a constant disassociation between 1 x 10-2 and 1 x 10-5 measured at a dilution of 40 liters per gram of molecule and a temperature of 25°C (eg lactic acid, glycolic acid, citric acid and ortho-phosphoric acid) in a regenerative process for the recovery of sulfur dioxide from the effluent gases.
[009] US Patent Application 4,366,134 (Korosy) discloses a regenerative flue gas desulfurization process using an aqueous solution of buffered potassium citrate at a pH of from about 3 to about 9.
[010] Organic solvents used in sulfur dioxide absorption/desorption processes include dimethyl aniline, tetraethylene glycol dimethyl ether and dibutyl butyl phosphonate. Like most solvents, the capacity of organic solvents is enhanced by higher pressures and lower temperatures. The sulfur dioxide gas is then recovered by reducing pressure and/or increasing temperature. These organic solvents require the use of metal construction and often require solvent regeneration due to the formation of sulfuric acid and in some cases due to the reaction of the solvent with sulfur trioxide formed by the side reaction of sulfur dioxide with oxygen during the absorption process /desorption. Organic solvents are generally more costly than aqueous absorption solutions.
[011] The significantly high flue gas flow rates emitted from a coal-burning power generation facility induce very large sizes of equipment to recover sulfur dioxide. Organic solvents that require metal construction generally do not compete economically well with wet scrubbers that typically use fiber reinforced plastic construction, coated containers, or low-cost alloys.
[012] Conventional organic solvents are also retarded by one or more failures in relation to desirable characteristics in an absorbent used in a sulfur dioxide absorption/desorption cycle. Many of these solvents have relatively low sulfur dioxide absorption capacity, especially at the sulfur dioxide partial pressures typically found in weak effluents that contain sulfur dioxide (eg, from about 0.1 to about 5 kPa). These solvents often absorb substantial amounts of water vapor from effluent containing sulfur dioxide which results in a significant reduction in the sulfur dioxide absorbing capacity of the solvent. As a result, the molar flow rates of these solvents necessary to satisfy the desired sulfur dioxide absorption efficiency are high. Furthermore, the absorption of large amounts of water vapor in the solvent can induce excessive corrosion of the process equipment used in the sulfur dioxide absorption/desorption process. Furthermore, some of these solvents are susceptible to excessive degradation, such as hydrolysis, or other side reactions or decomposition when the solvent is exposed to high temperatures in acidic environments and/or suffers from high volatility, inducing large solvent losses.
[013] Thus, there is a need for sulfur dioxide absorption processes and solvents and/or effective solutions for selective and energy efficient removal and recovery of sulfur dioxide from effluent gases. BRIEF DESCRIPTION OF THE INVENTION
[014] According to the present invention, an improved process for the selective removal of contaminants from effluent gases was elaborated. In some embodiments of the present invention sulfur dioxide is selectively removed and recovered from effluent gases in a sulfur dioxide absorption/desorption process that utilizes an aqueous buffered absorption solution comprising certain weak organic or inorganic acids or salts thereof, preferably certain polyprotic carboxylic acids or salts thereof, to selectively absorb sulfur dioxide from the effluent gas. The present invention also provides improved energy efficiency in regeneration of the absorption solution using an integrated sulfur dioxide extractor and heat pump system or vapor compression technique. Certain embodiments of the present invention relate to a process for simultaneously removing sulfur dioxide and nitrogen oxides (NOx) from effluent gases and recovering sulfur dioxide. Furthermore, the present invention provides a process for controlling the contaminating concentration of sulfate salt in the absorption solution by partial crystallization and removal of the sulfate salt crystals.
[015] Briefly, for this reason, the present invention is directed to a process for selectively removing and recovering sulfur dioxide from an effluent gas that contains sulfur dioxide. The process comprises placing an effluent gas containing sulfur dioxide in contact with an aqueous buffered absorption solution comprising sodium malate or metal salts of certain other weak polyprotic carboxylic acids in a sulfur dioxide absorber, which thereby absorbs the sulfur dioxide from the effluent gas in the absorption solution and produces an exhaust gas from which the sulfur dioxide is removed and an absorption solution enriched with sulfur dioxide. The sulfur dioxide enriched absorption solution is subsequently heated to desorb sulfur dioxide in a sulfur dioxide extractor and thereby produce a regenerated sulfur dioxide absorption solution and an extractant gas enriched with sulfur dioxide. The regenerated sulfur dioxide absorber solution is reintroduced into the sulfur dioxide absorber.
[016] The present invention is further directed to a process for selectively removing and recovering sulfur dioxide from an effluent gas containing sulfur dioxide in which the effluent gas and oxygen are in contact with an aqueous absorption solution buffered in a sulfur dioxide absorbent to produce an exhaust gas from which sulfur dioxide is removed and an absorption solution enriched with sulfur dioxide. The aqueous absorption buffer solution comprises a salt of a polyprotic carboxylic acid and an oxidation inhibitor selected from the group consisting of ascorbic acid, ethylenediaminetetraacetic acid, p-phenylenediamine, hydroquinone and mixtures thereof. The sulfur dioxide enriched absorption solution is subsequently heated to desorb sulfur dioxide in a sulfur dioxide extractor and thereby produce a regenerated sulfur dioxide absorption solution and an extractant gas enriched with sulfur dioxide. The regenerated sulfur dioxide absorber solution is reintroduced into the sulfur dioxide absorber.
[017] The present invention is also directed to a process for recovering sulfur dioxide from an aqueous absorption solution enriched with sulfur dioxide comprising a salt of a polyprotic carboxylic acid and used in regenerative recovery of sulfur dioxide to from an effluent gas. The process comprises heating the sulfur dioxide enriched absorption solution to desorb sulfur dioxide in a sulfur dioxide extractor and thereby produce a regenerated sulfur dioxide absorption solution and an extractant gas enriched with sulfur dioxide which comprises water vapor. Extractor gas enriched with sulfur dioxide is cooled in a high temperature overhead condenser of the sulfur dioxide extractor to condense water vapor and produce a high temperature overhead condenser gas effluent comprising sulfur dioxide sulfur and water vapor and an aqueous condensate comprising sulfur dioxide. The regenerated sulfur dioxide absorbing solution is heated in a reboiler of the sulfur dioxide extractor, wherein the upper high temperature condenser comprises a heat pump system evaporator in which a refrigerant is evaporated by heat transfer from of the extractant gas enriched with sulfur dioxide and the reboiler of the sulfur dioxide extractor comprises a heat pump condenser system in which the refrigerant is condensed by heat transfer to the regenerated sulfur dioxide absorption solution. Preferably, the regenerated sulfur dioxide absorbing solution is heated to a temperature less than about 20°C in excess of the temperature of the aqueous condensate. The aqueous condensate from the high temperature upper condenser is heated to desorb sulfur dioxide in a condensate extractor and produce a condensate extractor gas comprising water vapor and sulfur dioxide desorbed from the aqueous condensate. The condensate extractor gas and high temperature upper condenser gas effluent are cooled in a low temperature condenser to condense the water vapor and produce a stream of recovered sulfur dioxide comprising sulfur dioxide obtained from both the aqueous condensate and in the high temperature upper condenser gas effluent and an extracted condensate effluent emptied of sulfur dioxide.
[018] In an alternative embodiment of the present invention, the process for recovering sulfur dioxide from an aqueous absorption solution enriched with sulfur dioxide comprises heating the absorption solution enriched with sulfur dioxide to desorb sulfur dioxide to a sulfur dioxide extractor and thereby producing a regenerated sulfur dioxide absorption solution and an extractant gas enriched with sulfur dioxide comprising water vapor. The pressure of the extractant gas enriched with sulfur dioxide is high and the pressurized extractant gas enriched with sulfur dioxide is cooled by means of heat transfer to the regenerated sulfur dioxide absorbing solution in a reboiler of the sulfur dioxide extractor to condense the water vapor and produce a boiler gas effluent comprising sulfur dioxide and water vapor and an aqueous condensate comprising sulfur dioxide. Aqueous condensate from the reboiler is heated to desorb sulfur dioxide in a condensate extractor and produce a condensate extractor gas comprising water vapor and sulfur dioxide desorbed from the aqueous condensate. The condensate extractor gas and reboiler gas effluent are cooled in a low-temperature condenser to condense the water vapor and produce a stream of recovered sulfur dioxide that comprises sulfur dioxide obtained from the aqueous condensate and the gas effluent reboiler and an extracted condensate effluent emptied of sulfur dioxide.
[019] The present invention is also directed to a process of simultaneous removal of sulfur dioxide and NOx from an effluent gas that contains sulfur dioxide, which comprises NOx, and which recovers sulfur dioxide. The process comprises contacting the effluent gas with an aqueous buffered absorption solution comprising a salt of a polyprotic carboxylic acid, ascorbic acid and a metal chelator (metal complex) comprising a chelating agent and a metal cation in an absorbent that absorbs such Thus, the sulfur dioxide and NOx from the effluent gas in the absorption solution and produces an exhaust gas from which the sulfur dioxide and NOx have been removed and an absorption solution enriched with sulfur dioxide and NOx and comprising anion of bisulfite. The NOx absorbed in the absorption solution is then reduced to form nitrogen and bisulfate anion and the absorption solution is heated to desorb sulfur dioxide in a sulfur dioxide extractor and thereby produce a regenerated absorption solution and a extraction gas comprising sulfur dioxide and nitrogen. The regenerated sulfur dioxide absorber solution is reintroduced into the sulfur dioxide absorber.
[020] In yet another embodiment, the present invention is directed to a process of treating a regenerated sulfur dioxide absorption solution used in the regenerative recovery of sulfur dioxide from a sulfur dioxide containing effluent gas in which the regenerated absorption solution comprises a salt of a polyprotic carboxylic acid and sulfate salt and controls the sulfate salt concentration to an acceptable level. The process comprises treating an air stream from the regenerated absorption solution. More particularly, the process comprises providing an air stream wherein the air stream is a portion of the regenerated sulfur dioxide absorbing solution which evaporates water from the air stream at a temperature of at least about 40°C to produce a concentrated solution of supersaturated aqueous absorption in the sulfate sulfate salt. The sulfate salt crystals are heretofore precipitated from the concentrated aqueous absorption solution to form a crystallization slurry comprising precipitated sulfate salt crystals and a mother liquor. The sulfate salt crystals are then separated from the mother liquor to form a treated aqueous absorption solution comprising the polyprotic carboxylic acid salt.
[021] Other objects and features will be in part evident and in part pointed out hereinafter. BRIEF DESCRIPTION OF THE DRAWINGS
[022] Figure 1 is a schematic flowchart illustrating an embodiment of the process of the present invention for selectively removing and recovering sulfur dioxide from an effluent gas that contains sulfur dioxide and includes an integrated sulfur dioxide extractor and heat pump system; Figure 2 is a schematic flow diagram illustrating another embodiment of the process of the present invention for selectively removing and recovering sulfur dioxide from an effluent gas containing sulfur dioxide using vapor compression Figure 3 is a schematic flow diagram of the apparatus used in the batch absorber experiments described in Example 1; Figure 4 is a graph of the molar ratio of absorbed sulfur dioxide per mole of carboxylic acid salt as a function of dioxide concentration of sulfur in the gas phase to various carboxylic acid salts investigated in the batch sorbent experiments described in Example 1; Figure 5 is a fl. a schematic flow diagram of the apparatus used in the absorbent column experiments described in Example 2; Figure 6 is a schematic flow diagram of the apparatus used in the extractor experiments described in Example 3; and Figure 7a is a schematic flow diagram of a portion of the apparatus used in the continuous absorber and extractor experiments described in Example 5, which illustrates the apparatus through the absorbent.
[023] Figure 7b is a schematic flowchart of a portion of the apparatus used in the continuous absorber and extractor experiments described in Example 5, which illustrates the apparatus after the absorbent through the extractor.
[024] Corresponding reference characters indicate corresponding components in all drawings. DESCRIPTION OF PREFERRED ACHIEVEMENTS
[025] Improved sulfur dioxide absorption/desorption processes for the recovery of sulfur dioxide from effluent gases have been elaborated. The use of regenerative sulfur dioxide absorption/desorption allows for the selective removal and recovery of sulfur dioxide that may otherwise be emitted to the atmosphere. The recovered sulfur dioxide can be marketed as a product or used as part of the feed gas to a contact sulfuric acid plant for the production of sulfuric acid and/or oil or a Claus plant for the preparation of sulfur element. The present invention also provides processes with reduced energy requirements for the regeneration of a sulfur dioxide absorption solution and effective control of sulfate levels in the absorption solution.
[026] According to a preferred embodiment, the absorption solution used in the present invention comprises a buffered aqueous solution of a salt of a relatively weak polyprotic carboxylic acid, wherein a polyprotic carboxylic acid is a carboxylic acid having two or more protons which can be removed by reaction with a base. Since water is typically present in the effluent gas containing sulfur dioxide to be treated, such as a flue gas, the absorption solution preferentially lowers the water vapor pressure, thereby reducing the energy required to desorb the dioxide of sulfur, reducing the possibility of formation of salt precipitates, and generation of a gas enriched with sulfur dioxide of greater concentration. The acid salt must have a strong affinity for sulfur dioxide, as an acid salt absorbent for sulfur dioxide, to effectively remove sulfur dioxide from the effluent gas containing sulfur dioxide even in concentrations of a few ppm in an absorbent with one or more stages of theoretical equilibrium.
[027] Once absorbed, sulfur dioxide reacts with the acid salt in the absorption solution to form a complex. The absorbed sulfur dioxide can form bisulfite ions (HSO3-) and sulfite ions (SO32- ) in solution. Consequently, the solubility of the complex formed with sulfur dioxide (the corresponding bisulfite and sulfite) is preferable and highly temperature dependent so that relatively mild heating and/or reduced pressure can be used to release sulfur dioxide and regenerate the absorption solution for additional absorption of sulfur dioxide. The preferred absorption solution used in the practice of the present invention takes advantage of the acidity of sulfur dioxide to selectively absorb sulfur dioxide in the absorption solution in the presence of the other components of the effluent gas even at very low concentrations (20 ppm or less) and then release it easily by applying gentle heat and/or reduced pressure to the sulfur dioxide enriched absorption solution.
[028] The pKa values of the polyprotic carboxylic acids used in the absorption solutions are a key criterion for selecting an effective sulfur dioxide absorption solution. As the pKa value increases, the sulfur dioxide absorption capacity also increases, reducing the amount of absorption solution required and, in turn, reducing the size of the absorbent. However, higher pKa values can hinder the release of sulfur dioxide and regenerate the sulfur dioxide absorption solution with gentle heating and/or reduced pressure. In contrast, sulfur dioxide absorption capacity tends to decrease with pKa value, but it may facilitate the release of absorbed sulfur dioxide during heat regeneration. Consequently, in view of these considerations, the polyprotic carboxylic acid used in the sulfur dioxide absorption solution generally exhibits one or more pKa values that provide acceptable sulfur dioxide absorption capacity while minimizing the energy requirement for sulfur dioxide desorption with mild heating. More particularly, the pKa(s) value is preferably from about 3 to about 10 to 25°C, preferably from about 4 to about 7 to 25°C. Preferably, the absorption solution comprises the salt of a polyprotic carboxylic acid which has two or more carboxylic acid groups. Since polyprotic carboxylic acids are capable of undergoing a series of dissociations, each having a pKa value, at least one of the pKa values is from about 3 to about 10 to 25°C, preferably from about 4 to about 7 to 25°C. Preferred salts of polycarboxylic acids have other polar groups. Having polar groups in the acid salt contributes to improving water solubility and reducing water vapor pressure. The lower water vapor pressure, in turn, induces a gas enriched with sulfur dioxide that contains a higher concentration of sulfur dioxide.
[029] Examples of preferred polyprotic carboxylic acids for use in the absorption solution include malic acid, citric acid, phthalic acid, terephthalic acid, succinic acid, glutaric acid, tartaric acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid (EDTA). Examples of other suitable but less preferred carboxylic acids include nicotinic acid (niacin) and levulinic acid. The sulfur dioxide absorbing solution may comprise mixture of acid salt absorbents.
[030] Table 1 lists the pKa of various carboxylic acids and their salts suitable for use in the practice of the present invention.


[031] As described in more detail below, salts are formed in the buffered aqueous absorption solution by the reaction of a metal base (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) introduced into the absorption solution in amounts sufficient to neutralize at least some of the acid groups. Consequently, depending on the absorbent acid and base employed, salts present in the absorption solution include sodium or potassium malate, citrate (eg, hydrogen citrate, dihydrogen citrate), phthalate, terephthalate, succinate, glutarate, tartrate, nitrilotriacetate , ethylenediamine tetraacetate, nicotinate, levulinate, etc. According to a particularly preferred embodiment, the buffered aqueous absorption solution comprises sodium malate as the sulfur dioxide acid salt absorbent. Salts, such as sodium malate, suppress bisulfite oxidation and sulfate formation in the absorption solution.
[032] In order to maintain acceptable sulfur dioxide absorption capacity and minimize the energy requirement for the regeneration of the buffered aqueous absorption solution, the neutralization of the acid in the absorption solution after contact with the effluent gas containing sulfur dioxide sulfur is preferably controlled such that the acid is neutralized within about 20%, more preferably within about 10%, of the equivalence point of the acid group having a pKa value of from about 3 to about 10 to 25°C, preferably from about 4 to about 7 to 25°C. That is, the amount of base added to the absorption solution on a molar basis within 20% of the equivalence point, more preferably within 10% of the equivalence point, where the equivalence point is the number of moles needed to react from stoichiometric way it reacts with the acid group(s) that have(have) a pKa value within the desired range. Thus, at the equivalence point, the base amount added to the absorption solution, on a molar basis, is 100% of the stoichiometric amount to react with the acid group(s) that have (have) a pKa within the desired range , that is, complete neutralization.
[033] According to an especially preferred embodiment, acid groups having a pKa value of from about 3 to about 10 to 25°C, preferably from about 4 to about 7 to 25°C, are substantial and completely neutralized. In the case of an absorption solution comprising a polyprotic carboxylic acid which has two or more carboxylic acid groups with dissociation ability, it may be advantageous to neutralize the more acidic acid groups to form an acid weaker than the original acid having a higher pKa desirable within the desired range. For example, malic acid with a first pKa of about 3.4 and a second pKa of about 5.11 at 25°C can be neutralized with a base so that the more acidic carboxylic acid group is completely neutralized and the second, less acidic carboxylic acid group is neutralized within about 20%, more preferably within about 10%, of the acid dissociation equivalence point which has a pKa value of 5.11 at 25°C.
[034] Figure 1 is a schematic flowchart illustrating an embodiment of the process of the present invention for selectively removing and recovering sulfur dioxide from an effluent gas that contains sulfur dioxide.
[035] Effluent gas that contains sulfur dioxide can be derived from a variety of sources including: flue gas generated in the combustion of carbon sulfur fuels (eg, effluent from coal-burning power generation facilities); gaseous effluents from metal roasting operations; incinerator tail gas from a Claus plant; the exhaust gas of a sulfur trioxide absorbent from a contact sulfuric acid plant; and other systems where dilute sulfur dioxide streams can be emitted to the atmosphere or where sulfur dioxide must be removed prior to further treatment or use. As noted above, in some embodiments, the present invention is used for the recovery of sulfur dioxide from effluents relatively low in sulfur dioxide content. Thus, in accordance with an embodiment of the present invention, the effluent gas contains from about 0.01 to about 5% by volume of sulfur dioxide. However, it should be understood that the present invention can be employed to reduce the sulfur dioxide gas force of effluent gases where the sulfur dioxide concentration could be substantially greater than 5% by volume. In addition to sulfur dioxide, the effluent gas typically contains carbon dioxide, nitrogen oxides (NOx), oxygen, nitrogen and other inert components, and water vapor. In most cases, the effluent gas comprises water vapor. However, it should be understood that, in the practice of the present invention, the off-gas may alternatively be substantially anhydrous, for example, when the off-gas is the effluent of absorbent sulfur trioxide from a contact sulfuric acid plant.
[036] Typically, the effluent gas is at an elevated temperature and may contain entrained particulate impurities. In such examples, the effluent gas can be conditioned prior to being introduced to the sulfur dioxide absorbent by cleaning the gas to remove particulates and cooling the gas to maintain the desired temperature in the absorbent. Depending on the temperature and composition of the sulfur dioxide containing effluent gas, the effluent gas can be suitably conditioned by a variety of conventional practices known to those skilled in the art. For example, effluent gas may first be passed through a waste heat boiler where the gas is cooled by high pressure steam generation before being sequentially passed through a humidification tower and one or more indirect heat exchangers, where the gas is further cooled (eg with cooling tower water) and an electrostatic precipitator where the remaining particles are removed from the cooled gas. Alternatively, the effluent gas can be conditioned by passing the gas through one or more reverse jet cleaners of the type marketed by MECS, Inc., Saint Louis, Missouri 63178-4547 under the trademark DYNAWAVE.
[037] A waste heat boiler can be used to partially cool the effluent gas, such as a flue gas or a slurry gas, from a typical temperature around 140°C to a temperature close to the point of boiling the aqueous absorption solution (eg, about 100°C) and to provide heat for sulfur dioxide desorption. In another embodiment, a heat pump can be used to extract heat from the effluent gas and use the extracted heat in solvent regeneration. Furthermore, a pre-washer can be used for a variety of purposes including: reducing the temperature of the effluent gas that contains sulfur dioxide; saturate the effluent gas with water (minimizing changes in concentration in the absorbent solution); and to remove particulates and other components (eg mercury, chlorides, fluorides, etc.) present in the effluent gas that contains sulfur dioxide. After conditioning, the effluent gas is typically saturated with water vapor at a temperature of about 10°C to about 50°C.
[038] As shown in Figure 1, a sulfur dioxide containing effluent gas (10) is introduced into a sulfur dioxide absorbent (11) that has one or more theoretical stages in which it is in contact with an aqueous solution buffered absorption device comprising a salt of a polyprotic carboxylic acid as described above to absorb sulfur dioxide. The sulfur dioxide absorber (11) as shown is a vertical tower containing means for promoting mass transfer between the gaseous and liquid phases which may comprise a bed of random packs (not shown) such as saddles or rings, structured pack, or other contact device. The absorbent (11) may also be referred to herein as the absorbent tower (11). Preferably, in order to maximize the transfer of sulfur dioxide, the effluent gas (10) is otherwise contacted with the aqueous absorption solution. As shown in Figure 1, the effluent gas (10) is introduced through an inlet near the bottom of the absorbent tower (11) and the aqueous regenerated absorption solution (14) returned from the sulfur dioxide extractor (20) (defined later in the present document) is introduced through a liquid inlet near the top of the absorbent tower (11) and distributed over the pack (not shown). The sulfur dioxide enriched solution (16) is withdrawn from a liquid outlet near the bottom of the absorbent tower (11) and an exhaust gas stream (18) substantially free of sulfur dioxide is removed from a nearby outlet. to the top of the absorbent tower (11). Although a conventional randomly packed tower can be employed as an absorbent (11), those skilled in the art will appreciate that other configurations can be suitably employed. For example, the absorbent tower (11) can contain the structured package or comprise a tray tower, in any case the process streams preferably flow in the opposite way.
[039] The number of equivalent moles of acid salt absorbent present in the buffered aqueous absorption solution generally must be greater than the number of moles of sulfur dioxide to be recovered from the effluent gas (10) to compensate for various factors such as: the amount of sulfur dioxide remaining in the aqueous regenerated absorption solution (14) after regeneration of the absorption solution; the concentration of sulfur dioxide in the extractant gas enriched with sulfur dioxide; the possible presence of slightly acidic components such as carbon dioxide; but primarily to desirably compensate for the relatively poor absorption of the polyprotic salt/carboxylic acid absorption system (preferred to facilitate the desorption of sulfur dioxide via a mild increase in temperature and/or reduction in pressure). concentration of the polyprotic carboxylic acid/salt in the aqueous absorption solution necessary to obtain the desired removal efficiency will vary with the acid employed, the concentration of sulfur dioxide in the gas to be treated as well as the mass transfer characteristics of the absorbent and may be readily determined by someone skilled in the art. Typically, the molar ratio of sulfur dioxide absorbed per mole equivalent of polyprotic carboxylic acid salt in the absorption solution will range from about 0.1 to about 1. In the case of an absorption solution comprising the acid sodium salt malic acid to treat a gas comprising about 2600 ppmv (parts per million by volume) of sulfur dioxide, the concentration of malate in the absorption solution may suitably range from about 1% by mol to about 7% by mol. .
[040] Referring to Figure 1, the ratio (L/G) of mass flow rate of regenerated absorption solution stream (14) and effluent gas (10) required to carry out the substantial transfer of sulfur dioxide to from the effluent gas to the absorbent absorption solution (11) can be determined by conventional design practice. Preferably, the sulfur dioxide absorbent is designed and operated so that the sulfur dioxide content of the exhaust gas stream (18) exiting the absorbent (11) is less than about 500 ppmv, more preferably less than about 200 ppmv (eg as low as 10 to 20 ppmv). This trace amount of sulfur dioxide together with carbon dioxide, oxygen, nitrogen and other inert materials contained in effluent gas (10) are eliminated as part of the exhaust gas stream (18) expelled from the absorber top (11). The exhaust gas stream (18) is in substantial equilibrium with the absorption solution and, depending on the water vapor content of the effluent gas (10) and the conditions of the absorbent (11), there may be a net gain or loss. of water in the absorbent (11). If necessary, the blower (19) is used to direct the gases to the stack. In order to achieve satisfactory emission standards, the exhaust gas stream (18) can be passed through a mist eliminator or similar device (not shown) for recovery of entrained liquid before being discharged through a pile. Additionally or alternatively, in some cases the exhaust gas stream (18) may be heated by indirect heat exchange with the incoming process feed gas stream (10) or with the use of other heating means such that any feather will not have a tendency to descend after being emitted through the stack.
[041] The source of metal base composition (27) such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc., is combined with the regenerated absorption aqueous solution stream (14) introduced near the top of absorbent tower (11). The metal base (27) reacts with the polyprotic carboxylic acid to form the metal salt absorbent. In accordance with the above disclosure, sufficient metal base (27) is introduced to neutralize at least some of the acid groups so that the acid is neutralized to have about 20%, more preferably within about 10%, of the acid dissociation equivalence point having a pKa value of from about 3 to about 10 to 25°C, preferably from about 4 to about 7 to 25°C. One skilled in the art can use known pH control techniques and instrumentation to add base to the absorption solution by contacting the gas containing sulfur dioxide in the absorbent to maintain the desired degree of neutralization relative to the equivalence point of the value. pKa. Furthermore, sufficient base must be added to control the metal ion concentration. For example, as described below, some of the metal ions will be lost with the sulfate salt removed in a crystallizer operation. Two moles of base (eg sodium hydroxide) are added per mole of removed sodium sulfate. The metal ion concentration can be properly monitored and controlled by taking samples performing metal analysis in the installation laboratory.
[042] The absorption solution enriched with sulfur dioxide (16) leaving the absorbent (11) passes through the heat exchangers (24) where it is heated to an intermediate temperature. Additional heating can be provided by means of a waste heat boiler, a boiler, or any other external heat source such as live steam (not shown). The now preheated enriched solution (17) is introduced into the sulfur dioxide extractor (20) where the bisulfite reverts to sulfur dioxide and is dissolved from the solution. The extractor (20), as shown, is a vertical tower that contains means to promote mass transfer between the gas and liquid phases. As well as the absorber (11), the extractor (20) is shown in Figure 1 as configured in the form of a vertical tower, which contains means to promote mass transfer between the gaseous and liquid phases which may comprise a bed of random packages ( not shown) such as saddles or rings, structured package, trays or any other gas-liquid contact device. The extractor (20) may also be referred to herein as the extractor tower (20). The lower (depletion) section of the stripping tower (20) can be fed with steam and used to remove sulfur dioxide from the absorption solution and the top of the stripping tower (20) (reset section) is used to reduce the amount of water in sulfur dioxide. According to one embodiment, sulfur dioxide enriched solution (16) is heated by heat transfer from the effluent gas (10) and/or regenerated absorption solution (14) without the addition of external heat. In such an embodiment, the effluent gas temperature (10) preferably reduces to about 50°C and the difference in temperature between the preheated enriched solution (17) introduced into the extractor (20) and the regenerated absorption solution (14) is less than about 40°C. Extractor gas enriched with sulfur dioxide (23) is produced in the extractor top (20) and the regenerated absorption solution (14) is withdrawn from the extraction tower bottom (20) and sent back to the absorbent (11), completing the cycle. Although a conventional packaged tower can be employed, those skilled in the art will appreciate that the extractor (20), as well as the absorbent (11), can have other suitable configurations, including a tower that contains the structured package, trays or other delivery devices. contact.
[043] The average temperature of the sulfur dioxide absorption solution in the absorbent (11) will generally be maintained in the range of about 10°C to about 70°C. According to the present invention, the average temperature of the sulfur dioxide absorbing solution in the absorbent (11) is preferably maintained at about 20°C to about 60°C. Although, in general, the absorption of sulfur dioxide is enhanced at lower solution temperatures, the absorption solution needs to be heated from the absorption temperature to a sufficiently high temperature and/or under reduced pressure to release the sulfur dioxide and the supply of this sensible heat induces greater energy demands. During regeneration, it is also desirable to reduce the amount of water vaporized to decrease energy consumption and to avoid low concentrations of water in the liquid which can cause precipitation of weak polycarboxylic acid or salts. The overall efficiency of the sulfur dioxide absorption/desorption process is improved when absorption dependence absorption is more extremely temperature dependent and within a narrower temperature range between absorption and desorption stages of the cycle.
[044] The average temperature of the sulfur dioxide absorption solution in the extractor (20) will generally be maintained in the range of about 60°C until the boiling point of this solution at the operating pressure of the extractor (20).
[045] The absorption and desorption of sulfur dioxide can be accentuated by increasing or decreasing the operating pressures of absorbent (11) and the extractor (20), respectively. Suitable operating pressures in the absorbent (11) are from about 70 to about 200 kPa absolute. Pressure increases the amount of sulfur dioxide that the absorption solution can absorb, but absorption can be carried out at relatively low pressure, thereby reducing equipment costs. Similarly, suitable operating pressures in the extractor (20) are from about 40 to about 200 kPa absolute, but higher or lower operating pressures can be employed.
[046] The temperature control inside the absorber (11) and the extractor (20) can be performed by controlling the temperature of various process streams fed to these operations. Preferably, the temperature in the extractor (20) is kept within the desired range by controlling the temperature of the preheated enriched solution (17). Referring again to Figure 1, the sulfur dioxide enriched solution (16) exits the sorbent (11) at a temperature of from about 10°C to about 70°C, more preferably from about 20°C to about 60°C is passed through heat exchangers (24) where it is preheated to an intermediate temperature by indirect heat transfer from the regenerated absorption solution (14) which is recycled from the extractor (20) to the absorber (11). If additional heating is required in order to obtain the desired temperature in the extractor (20), the preheated enriched solution (17) can be passed through a solvent heater (not shown), and further heated by indirect heat exchange with steam . Steam can also be introduced near the bottom of the extractor (20). The regenerated absorption solution (14) exiting the extractor bottom (20) at a temperature of about 60°C to about 140°C is cooled in the exchanger (24) by means of heat transfer to the solution enriched with dioxide of sulfur (16) coming out of the absorbent (11). Similarly, if additional cooling is required in order to maintain the desired temperature in the absorbent (11), the regenerated absorption solution (14) leaving the exchanger (24) can be passed through the solvent cooler (26) and again cooled by indirect heat exchange with cooling tower water. The use of heat exchangers (24) reduces system energy demands so the use of a solvent heater and/or solvent cooler may not be required. SULFATE CONTAMINANT CONTROL / OXIDATION SUPPRESSION
[047] In regenerative processes, there is potential for accumulation of contaminants in the absorption solution that can interfere with the absorption/depletion operations. The predominant contaminant is sulfate salt together with other sulfur-containing species such as thiosulfates and thionates and acid gases absorbed from the effluent gas to be treated. Sulfur dioxide containing effluent gas often contains some sulfur trioxide as well as sulfuric acid haze. Additionally, liquid phase oxidation of sulfur dioxide absorbed in the absorbent induces the formation of sulfuric acid.
[048] Oxidation tends to be highly temperature dependent and increases sharply as the temperature in the absorbent increases. The addition of a base (eg NaOH) restores the buffering capacity of the absorption solution by neutralizing sulfuric acid and forming sulfate salts (eg Na2SO4) that accumulate in the absorption solution. Thus, there is a need for a method of treating an aqueous absorption solution used in regenerative recovery of sulfur dioxide to control sulfate contaminants to an acceptable level with minimal absorbent losses and without considerable consumption of buffering agents or steps. complex processes that would undermine the economic viability of the process.
[049] According to one embodiment of the present invention, the levels of sulfate salt contaminant in an aqueous absorption solution comprising a salt of a polyprotic carboxylic acid are controlled to an acceptable level by periodically diverting at least a portion of the solution from regenerated absorption coming out of the treatment extractor to remove sulphate as a stream of air. The treatment comprises evaporating water from a stream of air to produce a concentrated solution supersaturated in the sulfate sulfate salt. The sulfate salt crystals are then precipitated from the concentrated aqueous absorption solution in a crystallizer to form a crystallization slurry comprising precipitated sulfate salt crystals and a mother liquor. Concentration of the aqueous absorption solution can suitably be achieved by heating and/or reducing the pressure to instantly evaporate the water. Typically, the aqueous absorption solution is heated to a temperature of at least about 40°C, more preferably at least about 60°C and preferably to the boiling point of the absorption solution in the extractor at the operating pressure of the extractor, during the concentration to inhibit the formation and precipitation of sodium sulfate decahydrate or Glauber's salt (Na2SO4-10H2O).
[050] As shown in Figure 1, the air stream (30) of the regenerated absorption solution (14) leaving the extractor (20) at a temperature of about 60°C to about 140°C can be heated in the preheater (32) of the crystallizer to evaporate the water and produce the concentrated aqueous absorption solution (34) supersaturated in the sulfate salt. The concentrated solution (34) is directed to the crystallizer (36) to precipitate the sulfate salt crystals from the concentrated solution (34) and form a crystallization slurry comprising precipitated sulfate salt crystals and a mother liquor. Crystallizer (36) can be operated at atmospheric pressure or under vacuum. The sulfate crystals can be separated from the mother liquor by conventional solid-liquid separation equipment such as a centrifugal or vacuum filter. Alternatively or additionally, the crystallizer can be designed to continuously decant the mother liquor from the crystallization slurry. The crystallizer (36) is operated at temperature and pressure to remove sulfate salt and control the concentration of sulfate salt in the absorption solution at levels cited below herein.
[051] As shown in Figure 1, the upper stream (38), which contains the mother liquor, can be directed to the solvent cooler (26) and combined with the remainder of the regenerated absorption solution (14) that is introduced at the top of absorbent tower (11). Furthermore, the sulfate salt crystals can be washed with water and the resulting wash water comprising the polyprotic acid salt absorbent directed similarly to the absorbent (11). The upper stream (38) from the crystallizer (36) can be condensed and returned to the absorber (11). Alternatively, the upper stream (38) from the crystallizer (36) can be addressed to the extractor (20) as a source of exhaust vapor.
[052] Although the treatment described above is effective to control acceptable levels of sulfate salt in the circulating absorption solution, in accordance with some embodiments of the present invention, an oxidation inhibitor can be included in the absorption solution to reduce bisulfite oxidation and sulfite to bisulfate and sulfate contaminants, respectively. There are several different types of oxidation inhibitors that may be useful in the practice of the present invention, which include: oxygen detoxifying elements and free radical scavengers such as p-phenylenediamine and hydroquinone; NOx catalyzed oxidation inhibitors such as ascorbic acid; and chelating agents such as ethylenediaminetetraacetic acid (EDTA) which sequester and inhibit catalyzed metal oxidation. Such oxidation inhibitors can be employed singly or in various combinations and can be added as needed to the aqueous regenerated absorption solution introduced to the absorbent. Depending on the type of inhibitor(s) employed, the concentration in the absorption solution typically ranges from a few ppm to about 1 to about 10 percent by weight. An excess is typically added (eg at least about 1000 ppm) as the inhibitors will gradually be consumed by oxidation. Ascorbic acid and hydroquinone are particularly effective in inhibiting oxidation in a sodium malate absorption solution. EDTA is expected to be effective as an oxidation inhibitor when metals are present in the absorption solution.
[053] The high acidity in the absorption solution has the effect of raising the sulfur dioxide depletion efficiency. Thus, leaving a small concentration of sulfur dioxide or sulphate salt dissolved in the absorption solution induces greater extractor efficiency. For example, a small concentration of sodium sulphate and/or sulfuric acid in the extractor makes the regeneration of the absorption solution less energy intensive. According to one embodiment of the invention, the concentration of the sulfate salt is controlled at from about 0.5 to about 11 percent by weight, preferably from about 3 to about 11 percent by weight in the absorption solution and a a small fraction of sulfur dioxide is left in the aqueous regenerated absorption solution thereby making the solution slightly more acidic and consequently making the desorption of sulfur dioxide less energy intensive.SULFUR DIOXIDE RECOVERY/ENERGY INTEGRATION
[054] As noted above, steam is the preferred exhausting agent for removing the relatively non-condensable sulfur dioxide absorbed in the sulfur dioxide enriched solution, although other components, such as clean exhaust gas, may be employed during solvent regeneration. Steam can be supplied by re-boiling the sulfur dioxide enriched solution in an extractor boiler and/or by injecting live steam into the base of an extractor column. The steam provides the energy required to heat the solution enriched with sulfur dioxide to desorb the dissolved sulfur dioxide and serves as a diluent for the removed gases, which increases the drive force for desorption and sweeps the dissolved sulfur dioxide from the tower of depletion. The steam is readily separated from the sulfur dioxide-enriched extractant gas by condensation in an overhead condenser. However, such separation from exhaust steam is wasteful as it involves condensing water vapor and present loss of latent heat to the condenser cooling medium (eg, cooling water) and external energy needs to be supplied from to generate additional steam. Consequently, it is important to reduce the energy requirement of the depletion operation as much as possible.
[055] The energy efficiency of a depletion operation can be improved by using heat pumps to extract energy from the extractant gas enriched with sulfur dioxide at the condensing temperature and return it to the process in the reboiler. The energy efficiency of a depletion operation can also be improved by using a vapor compression technique in which the extractant gas enriched with sulfur dioxide is mechanically compressed and subsequently condensed with the recovery of latent heat for use in reboiling the solution. of depleted absorption. The use of heat pumps and vapor compression techniques to reduce the energy requirement of the exhaust operation are disclosed in US patent application 4,444,571 (Matson) and US patent application 4,181,506 (Bengtsson).
[056] Although a heat pump system can potentially reduce the energy requirement of the sulfur dioxide extractor, such systems are economically viable when the temperature differential between the heated regenerated sulfur dioxide absorbing solution in the reboiler and the condensate of the upper condenser is not greater than about 20°C. As the temperature differential narrows, heat pump systems become even more attractive in providing energy savings.
[057] An integrated sulfur dioxide extractor and heat pump system capable of providing improved energy efficiency has been designed. In the integrated system, the exhaust vapor condensation of the extractant gas enriched with sulfur dioxide is split between an upper high temperature condenser and a subsequent condenser operated at a lower temperature. In the high temperature condenser, most of the water vapor is condensed (and most of the latent heat removed) which represents the main part of the heat of condensation. In order to enhance the energy efficiency of the heat pump system, the temperature of the condensate should be less than about 20°C lower than the temperature in the extractor reboiler. Preferably, more than about 50% of the latent heat is removed in the high-temperature upper condenser without decreasing the condenser temperature to less than about 20°C relative to the temperature in the boiler. Preferably, the differential between the temperature of the condensate produced in the high temperature condenser and the reboiler temperature is less than about 15°C, even more preferably less than about 10°C. The high temperature upper condenser effluent gas comprising sulfur dioxide and water vapor gas is subsequently cooled to a temperature typically below about 70°C using cooling water or other cooling source in which the remaining water is condensed . As compared to conventional approaches, (without splitting the condensate), the temperature differential between the condensate and the reboiler can be kept small enough to allow efficient operation of the heat pump system.
[058] The integrated sulfur dioxide extractor and split-condensing heat pump system for recovering sulfur dioxide from an aqueous absorption solution enriched with sulfur dioxide is shown in Figure 1. As described above, the solution enriched with sulfur dioxide (16) is heated in the sulfur dioxide extractor (20) to desorb the sulfur dioxide and produce an aqueous regenerated absorption solution (14) and the extractant gas or higher enriched with sulfur dioxide (23) which comprises water vapor. The extractant gas enriched with sulfur dioxide (23) is cooled in the upper high temperature condenser (40) of the sulfur dioxide extractor (20) to condense a portion of the water vapor contained therein and produce the gas effluent. high temperature upper condenser (42) comprising sulfur dioxide and residual water vapor and aqueous condensate (44) comprising dissolved sulfur dioxide. A portion of the regenerated absorption solution (14) collected in the extraction tower well (20) is heated in the reboiler (46) of the sulfur dioxide extractor (20).
[059] As shown in Figure 1, an integrated heat pump system comprising a compressor/expansion valve assembly (48) is associated with the upper high temperature condenser (40) and the reboiler (46). high temperature upper condenser (40) comprises a heat pump system evaporator (not shown) in which a refrigerant or working fluid is evaporated by heat transfer from the sulfur dioxide enriched extractant gas (23) and the reboiler ( 46) of sulfur dioxide extractor (20) comprises a heat pump condenser system (not shown) in which the refrigerant or working fluid is condensed by heat transfer to the regenerated absorption solution (14). As noted above, the upper high temperature condenser (40) is operated to remove more than about 50% of the latent heat while maintaining a temperature differential of less than about 20°C between the condensate (44) and the reboiler (46) . The most efficient operation of the heat pump system is accomplished by keeping the differential between the high temperature condensate (44) and the reboiler (46) at no more than about 15°C, or even more preferably, no more than about 10°C (for example, the condensate temperature (44) is about 100°C and the boiler temperature (46) is about 106°C).
[060] The aqueous condensate (44) from the upper high temperature condenser (40) is fed to the condensate extractor or water column (50) and heated (eg with steam or a second boiler (not shown)) to desorb the sulfur dioxide and produce the condensate extracting gas (53) which comprises the water vapor and sulfur dioxide removed from the aqueous condensate (44). The condensate extractor gas (53) exiting the top of the condensate extractor column (50) is combined with the high temperature upper condenser gas effluent (42) and cooled in a low temperature condenser (54) (for example , with cooling water at 50°C) to condense the water vapor and produce recovered sulfur dioxide stream (56) which comprises sulfur dioxide obtained in the aqueous condensate (44) and in the high-top condenser gas effluent temperature (42). Separated condensate effluent (58) emptied of sulfur dioxide exits the bottom of the condensate extractor column (50) and can be combined with the regenerated absorption solution (14) and returned to the absorbent (11) or fed to the extractor base (20), or optionally a portion may be purged from the system.
[061] The integrated sulfur dioxide extractor and heat pump system shown in Figure 1 includes a separate extractor column (20) and the condensate extractor column (50). However, it should be understood that the extractor column (20) functions as the exhaust section and the condensate extractor column (50) function as the rectifying section so that the two columns could alternatively be integrated into a single column in which the solution enriched with sulfur dioxide (16) is fed to a few trays below the low temperature condenser (54).
[062] According to an alternative embodiment of the present invention, a vapor compression technique is used in conjunction with splitting the exhaust vapor condensation of the sulfur dioxide enriched extractant gas between the reboiler of the sulfur dioxide extractor and a subsequent condenser operated at a lower temperature. This vapor compression realization also provides marked energy efficiency, but as compared to the integrated sulfur dioxide extractor and heat pump system realization shown in Figure 1, this alternative realization can reduce capital cost by eliminating the high-top condenser. temperature and the compressor/expansion valve assembly.
[063] The embodiment using vapor compression and split condensation to recover sulfur dioxide from an aqueous absorption solution enriched with sulfur dioxide is shown in Figure 2, in which numbers not described below in this document have the same meaning as the numbers in Figure 1. As described above, the sulfur dioxide enriched solution (16) is heated in the sulfur dioxide extractor (20) to desorb the sulfur dioxide and produce the aqueous regenerated absorption solution ( 14) and the extracting or higher gas enriched with sulfur dioxide (23) comprising water vapor. The pressure of extractant gas enriched with sulfur dioxide (23) exiting the extractor (20) is increased, for example, by mechanical compression in the compressor (60). Alternatively, if higher pressure steam is available, a steam ejector or similar device (not shown) can be used to increase the pressure of extractant gas enriched with sulfur dioxide (23). Typically, the pressure rise is from about 45 kPa to about 65 kPa. Furthermore, it is typically preferred to operate the extractor (20) at lower pressures (eg under vacuum) to increase the relative volatility of sulfur dioxide relative to water and enhance desorption (eg fewer theoretical stages needed for a given reflux). Additionally, the lower pressures induce lower temperatures in the system, allowing the use of lower pressure steam to heat the solution enriched with sulfur dioxide (16). However, the vacuum operation of the extractor (20) increases the extractor diameter (20) and the associated capital cost. By way of example, operating the extractor (20) under a slight vacuum (eg the measure of -35 kPa) and modestly increase the pressure of extractant gas enriched with sulfur dioxide (23) exiting the extractor (20) (eg measuring around 20 kPa) will represent an economical approach. However, operating the extractor (20) at or above atmospheric pressure can also be an attractive approach. Economic optimization can determine specific operating conditions.
[064] The pressurized flow of gas containing sulfur dioxide (61) is directed to the reboiler (46) where a substantial portion of the steam is condensed and the latent heat is transferred to heat a portion of the regenerated absorption solution (14) collected in the extraction tower well (20). In the reboiler (46) most of the water vapor is condensed (and most of the latent heat removed) which represents the main part of the heat of condensation. Preferably, more than about 50% of the latent heat is removed in the reboiler (46). Reboiler gas effluent (62) comprising sulfur dioxide and waste water vapor gas is removed from the reboiler (46) and subsequently cooled to a temperature typically below about 70°C using cooling water or other source of cooling in which the remaining water is condensed. Aqueous condensate (64) comprising dissolved sulfur dioxide from the reboiler (46) is fed to the condensate extractor or water column (50) and heated (e.g., with steam or a reboiler, not shown) to desorb the nitrogen dioxide. sulfur and produce condensate extracting gas (53) which comprises water vapor and sulfur dioxide desorbed from the aqueous condensate (64). The condensate extractor gas (53) exiting the top of the condensate extractor column (50) is combined with reboiler gas effluent (62) and cooled in the low temperature condenser (54) (eg with cooling water at 50°C) to condense the water vapor and produce recovered sulfur dioxide stream (56) which comprises sulfur dioxide obtained from the aqueous condensate (64) and the reboiler gas effluent (62). The separated condensate effluent (58) emptied of sulfur dioxide exits the bottom of the column of the condensate extractor (50) and can be combined with the regenerated absorption solution (14) and returned to the absorbent (11) or fed to the base. extractor (20), or optionally a portion may be purged from the system. SIMULTANEOUS REMOVAL OF SULFUR AND NOX DIOXIDE
[065] NOx emissions are present in most effluent gases in which sulfur dioxide is also present. NOx is often present at concentrations lower than sulfur dioxide. By “NOx” is represented herein one or more oxides of nitrogen, such as nitric oxide (NO), and nitrogen dioxide (NO2). Nitric oxide slowly reacts with oxygen to form nitrogen dioxide. The oxidation of nitric oxide to nitrogen dioxide is extremely favored by lower temperatures so that the reaction rate increases as the temperature is lowered. At ambient temperatures, the ratio of NO to NO2 approaches one. At higher temperatures, nitric oxide is present in a higher ratio.
[066] A further aspect of regenerative recovery of sulfur dioxide according to another embodiment of the present invention is the simultaneous removal of sulfur dioxide and NOx from an effluent gas containing sulfur dioxide, which comprises NOx. Ascorbic acid increases the absorption of any nitrogen dioxide in the absorption solution. It is believed that salt-absorbing polyprotic carboxylic acids (eg, sodium malate) will also increase NO2 absorption in a manner analogous to sulfur dioxide absorption. The addition of metals such as Fe+2 or Co+2 in the presence of a polybasic acid chelating (eg EDTA) induces the formation of a metal complex which is particularly effective in absorbing nitric oxide. Ascorbic acid, polybasic acid and active metal can be added as needed to the absorbing solution of regenerated polyprotic carboxylic acid salt introduced into the absorbent. Since both nitrogen dioxide and nitric oxide are absorbed into the absorption solution, sufficient residence time is provided to allow for the oxidation of bisulfite to bisulfate and the reduction of nitric oxide and nitrogen dioxide to nitrogen. By selecting the appropriate concentrations of ascorbic acid, the metallic chelating agent and active metal and allowing the reaction that takes place in the process of the present invention to be configured to remove nitric oxide and nitrogen dioxide.
[067] Figure 1 shows a potential process diagram for the simultaneous removal of sulfur dioxide and the reaction of NOx to nitrogen and sodium sulfate. In particular, the NOx reactor (15) receives at least a portion of the solution enriched with sulfur dioxide (16) which comprises a salt of a polyprotic carboxylic acid, ascorbic acid and a metal chelator or metal complex comprising a chelating agent and a metallic cation. Suitable chelating agents include ethylenediaminetetracarboxylic acid (eg EDTA) or other polybasic acid. Reactor (15) provides sufficient residence time for the reduction of nitric oxide and nitrogen dioxide to nitrogen. Any sulfate formed is removed in the crystallizer (36). This approach is particularly attractive since it allows the simultaneous removal of two air pollutants using one system.
[068] The recovered sulfur dioxide stream (56) can be used to prepare element sulfur by Claus process or further cooled to condense sulfur dioxide into a liquid product. For example, the off-gas containing sulfur dioxide can comprise off-gas from the incinerator of a Claus plant and the recovered sulfur dioxide stream can be recycled to the inlet of the Claus incinerator. Alternatively, the recovered sulfur dioxide can be fed to a contact sulfuric acid plant so that the sulfur dioxide contained in the stripper gas is finally recovered as sulfuric acid and/or concentrated oil. The process of the present invention is particularly useful in altering the composition of an effluent gas relatively weak in sulfur dioxide (e.g., about 0.01 to about 5 percent by volume) and having a molar ratio of H2O/SO2 greater than the molar ratio of H2O/SO3 in the desired acid product so as to provide a gas enriched with sulfur dioxide that has a composition suitable for the conversion of concentrated to concentrated sulfuric acid and/or oil in a contact sulfuric acid plant .EXAMPLES
[069] The Examples below are simply intended to further illustrate and explain the present invention. The examples, for this reason, should not be associated as a limitation on the scope of the invention or on the manner in which it may be practiced.EXAMPLE 1 - BATCH ABSORBENT EXPERIMENTS
[070] The following experiments were conducted in a batch absorber in which a gas containing sulfur dioxide was fed through a watering can below the liquid level into a reservoir containing an aqueous absorption solution comprising various salts of polyprotic carboxylic acid and the exhaust gas composition was monitored. A schematic of the experimental apparatus is shown in Figure 3.
[071] The inlet gas containing sulfur dioxide (101) to be treated comprised nitrogen saturated with water vapor and a controlled concentration of sulfur dioxide. Temperatures (T) and pressure (P) were monitored during the experiment and gas samples (S) were taken at different times during the experiment. T1 and p1 are inlet gas pressure and temperature sensors (101). s1 is a sampling point for the inlet gas (101). T2 is a temperature sensor for the liquid in the reservoir. T3 is an exhaust gas temperature sensor (102).
[072] In these experiments and other experiments reported in the Examples below, gas concentrations were measured by gas chromatography and liquid concentrations were calculated by material equilibrium.
[073] The graph in Figure 4 shows selected results from batch absorbent experiments under various conditions for absorption solutions comprising sodium malate (Na Mal) and sodium citrate (Na Cit). These results are expressed as the molar ratio of absorbed sulfur dioxide per mole of carboxylic acid salt as a function of the concentration of sulfur dioxide in the gas phase. The temperatures of these batch experiments were in the range of 25°C to 100°C, as shown in Figure 4 by the legend. All experiments were carried out at atmospheric pressure. These experiments address equilibrium concentrations and, in some cases, equilibrium data (called Eq. in the legend) are also included in the results shown graphically. For these equilibrium data, the gas and liquid compositions were diluted with excess caustic to keep sulfur dioxide in solution.
[074] Additional salt balance data results are provided in Table 2.

[075] Na = sodium; K = potassium; Mal = malate; Cit = citrate; Suc = succinate; Pha = phthalate.
[076] Total sulfur content was determined using ASTM Standard D1552, "Standard Test Method for Sulfur in Petroleum products (High-Temperature Method", DOI: 10.1520/D1552-08, available from ASTM International, West Conshohocken, PA, www.astm.org.
[077] A good absorption system is one that shows a good dependence on solubility or loading as a function of temperature.EXAMPLE 2 - ABSORBENT COLUMN EXPERIMENTS
[078] In the following experiments, a gas comprising nitrogen and oxygen saturated with water and containing sulfur dioxide was contacted with an absorption solution in a column of upstream absorbent.
[079] A schematic of the experimental apparatus is shown in Figure 5. The extemporaneous absorption solution (201) was introduced to the absorbent column (202). The upstream absorber column (202) was equipped with 1.92 meters (75.5 inches) of structured package and was operated at a temperature of 33.4°C and at atmospheric pressure (1 atm = 101.3 kPa ). The inlet gas (203) was introduced to the bottom of the absorbent column (202). The exhaust gas (204) was removed from the top of the absorbent column (202). The inlet gas (203) and exhaust gas (204) compositions were monitored and are reported in Table 3. The scavenger solution (201) comprised an aqueous solution of sodium malate and ascorbic acid as an oxidation inhibitor. In the experiments, gas samples could be taken along the absorbent column (202) through various sampling ports (not shown) to follow the decrease in sulfur dioxide concentration throughout the column. The sulfur dioxide enriched absorption solution (205) was removed from the absorbent column bottom (202). A small concentration of sulfur dioxide in the liquid phase was present reflecting partial depletion during the regeneration of sulfur dioxide enriched absorption solution (205).


[080] The results of this experiment show a 99.8% removal of sulfur dioxide from the inlet gas. The sulfur dioxide concentration decreased from 2% mol to 39 ppm after treatment. The sulfur dioxide concentration in the liquid outlet was about 4.4% by weight.EXAMPLE 3 - EXTRACTOR EXPERIMENTS
[081] In the following experiments an absorption solution enriched with sulfur dioxide was depleted to remove sulfur dioxide by heating the solution.
[082] A schematic of the experimental apparatus is shown in Figure 6. The Feed Reservoir (301) contains the absorption solution enriched with sulfur dioxide (302) collected during the absorption experiments. The absorption solution (302) comprised an aqueous solution containing 24% sodium malate and 3.7% by weight sulfur dioxide. The absorption solution (302) was fed as well as monitored by burette (303) at a rate of 47.2 grams/minute with the use of the first positive displacement pump (304) to the extractor column (306). The absorption solution (302) was pumped through the first pump (304) and preheated in a heated batch (305) and fed to the extractor column (306) consisting of 35 trays. The top (307) portion of the extractor column (306) contained 25 trays (stages) and the bottom portion (308) of the extractor column (306) contained 10 trays (stages).
[083] The extractor column (306) was operated at atmospheric pressure (1 atm = 101.3 kPa) and positioned above the boiler (309). Boiler (309) and top product (310) temperatures were maintained at 105°C and 100.2°C, respectively. The product top (310) comprised the liquid and gas at a liquid flow rate of 22.1 grams/minute of an aqueous solution containing 3% by weight of sulfur dioxide and a gas flow rate of 1 .45 g/minute of a mixture that contains 43% sulfur dioxide and 57% water. Temperature and pressure were measured and samples taken at various sample points (not shown). The top part of product (310) was condensed in the condenser (311), which was connected to vacuum (312). The exhaust gas (not shown) was subjected to flushing and retention. The liquid product was collected in the reservoir (313) for storage or recycling through the valve (314).
[084] The water from the water reservoir (315), which is the depleting agent, was fed to the extractor column boiler (309) (306) through pumps (316) and (317) at a rate of 24, 5 grams/minute as monitored by burettes (318) and (319). The water was heated by the heat exchanger (320) using the thermal tape. The treated absorption solution (321) was removed from the boiler (309) at a rate of 48.2 grams/minute which has a residual concentration of 0.93% by weight sulfur dioxide through the cooler (322) and the pump ( 323) to the absorption solution collection reservoir (324). This represented a 74% recovery of the sulfur dioxide fed to the column. The results are reported in Table 4.


[085] The following experiments were conducted in a batch crystallizer used to reduce the concentration of sodium sulfate formed by oxidation in an aqueous absorption solution comprising sodium malate. Water was removed from the boiler of a crystallizer by evaporation either under vacuum (4.4 psia, 0.3 atm, 30.3 kPa) at 75°C or at atmospheric pressure ((14.7 psia), 1 atm, 101 .3 kPa) at 106°C. Solids were separated (after evaporation and crystallization) from the liquid using a centrifuge filter. The initial composition of the aqueous absorption solution and crystallization conditions are shown in Table 5.


[086] About 64% of the water was removed in the vacuum experiment and about 66% of the water was removed in the atmospheric experiment. About 72% of the anhydrous sodium sulfate was removed from the original absorption solution and less than 1% of the sodium malate was lost with the removed sodium sulfate.EXAMPLE 5 - CONTINUOUS ABSORBENT AND EXTRACTOR EXPERIMENTS
[087] In the following experiments, a gas containing sulfur dioxide was fed to an absorbent column and contacted with an aqueous absorption solution comprising sodium malate and ascorbic acid as an oxidation inhibitor to produce an exhaust gas from which sulfur dioxide had been removed and an absorption solution enriched with sulfur dioxide which was then continuously regenerated in an extractor and returned to the absorbent column.
[088] A schematic of the continuous absorber and extractor system used in this Example is shown in the Figures. 7a and 7b. Figure 7a shows the operation of the system and the configuration and connections between the absorbent along the absorbent. The system is continued in Figure 7b after the absorber to the extractor, where the separation of the figure takes place for purposes of clarity. The absorption solution was used to remove sulfur dioxide from the inlet gas and then regenerated to the extractor. Each component designated “P” is a pressure measurement used to monitor pressure in the system.
[089] Both the absorber (562) and the extractor (602) were operated at atmospheric pressure (1 atm, 101.3 kPa). Nitrogen gas (which contains about 8% oxygen) (501) was fed from the nitrogen reservoir (500) through the compressor (502) and mass flow controller (503) and then preheated by the heat exchanger (504) connected to a hot tub (505) and fed to the water saturator (506) through the nitrogen gas inlet (507), protected by the safety valve (508). The water (521) was fed from the water reservoir (520) as monitored by the burette (522) through the pump (523) to the heat exchanger (524) which is connected to the heated water bath (525) via the water inlet (526) to the top of the water saturator (506). Nitrogen gas (501) is saturated with water (521) in the water saturator (506) to provide water-saturated Nitrogen gas (527).
[090] Water can be recycled from the water saturator bottom (506) through the valve (528) and the pump (529) back to the water reservoir (520). Alternatively, water can be recirculated to the water saturator through conduit (530). Yet another alternative is to remove water from the system through the valve (531) and the drain (532).
[091] Sulfur dioxide gas (541) was fed from the sulfur dioxide reservoir (540) through the compressor (542) and the mass flow controller (543) to combine with water-saturated nitrogen gas ( 527) and mixed in the static mixer (544) to achieve the desired sulfur dioxide concentration in the sulfur dioxide-containing absorbent inlet gas (545).
[092] Sodium malate/water absorption solution (551) was fed from the sodium malate/water feed tank (550), as monitored by the burette (552) to the heat exchanger (553), which was connected the hot tub (525), and then through the pump (554) and valve (555), through the inlet solution (556) to the top of the absorbent column (562).
[093] The gas containing sulfur dioxide (545) was fed through the inlet gas (546) and contacted otherwise with the absorption solution (551), which was fed through the inlet solution (556) to the column of absorbent (562) equipped with 1.92 meters (75.5 inches) of structured package and maintained at a constant temperature of 30°C using a heated box (not shown). Temperature was measured along the absorbent column (562) and samples could be collected along the absorbent column (562) to monitor the sulfur dioxide concentration (not shown).
[094] The flow rate of gas containing sulfur dioxide (545) to the sorbent column (562) was 24.3 g/minute. This flow rate was sufficient to handle the standard gas flows of 6.311 liters per hour (l/hour) and to reduce the sulfur dioxide concentration in the gas containing sulfur dioxide (545) (inlet gas) by 2,600 ppm at about 8.5 ppm in exhaust gas (584). The absorption solution removed 99.5% of the sulfur dioxide in the inlet gas.
[095] The sulfur dioxide-enriched absorption solution (565) containing the absorbed sulfur dioxide can be circulated back to the absorbent column (562) through the conduit (566) or through the valve (567) to either the reservoir collection (568) and the supply reservoir (570), whereby the solution (565) can be stored in the collection container for SO2 rich organic salt solution (569). The absorbent column (562) operates using a vacuum (589). Vacuum (589) can be used to control the removal of exhaust gas (584) from the absorbent column (562) through valve (585) to the condenser (586) and the liquid cooler (587).
[096] The sulfur dioxide in the enriched absorption solution (565) was removed and the solution regenerated to the extractor (602) equipped with 45 sieve trays. The sulfur dioxide-enriched absorption solution (565) containing the absorbed sulfur dioxide was filled and collected in the feed reservoir (600), then preheated and fed to the top of the extractor column (602). Sulfur dioxide-enriched absorption solution (565) was fed from the feed reservoir to the pump (604) as monitored by the burette (603) to be heated by the hot tub (605). The heated absorption solution (609) was fed to the extractor column (602) which has the head splitting top (606), intermediate feed section (607) and the lower tray section (608) which has 20 trays ( stages).
[097] The extractor column (602) was positioned above the boiler (610). The product top (611) comprised liquid and gas. Temperature and pressure were measured and samples taken at various sample points (not shown). The top part of product (611) was condensed in the condenser (612), which was connected to vacuum (613). The exhaust gas (614) is passed through a hydrogen peroxide/ice trap (615). The liquid product (616) was collected in the reservoir (617) for storage or recycling through the valve (618).
[098] The water from the water reservoir (624), which is the depletion agent, was fed to the extractor column boiler (609) (602) through the pump (626), as monitored by the burette (628) to maintain the concentration of water throughout the column (602). The water was heated using the heat exchanger (630) with the thermal strip. A portion of sulfur dioxide absorption solution (631) was removed from the boiler (609) through the condenser (632) and from the pump (633) through the valve (635) to the absorption solution collection reservoir (634). Alternatively, a portion of sulfur dioxide absorption solution (631) could be transferred through the pump (633) and valve (635) to the sodium malate/water feed tank (550).
[099] The extractor column (602) and boiler (609) were operated so that the temperature at the base of the extractor column (602) was 106.4°C and 100.2°C at the top of the extractor (602).
[0100] The exhaust gas stream (614) and the liquid product (616) was removed from the top of the extractor column (602). The gas stream (614) had a concentration of about 62% sulfur dioxide and the liquid product (616) had a concentration of 0.93% by weight sulfur dioxide. The portion of sulfur dioxide absorption solution (631) containing 0.53% by weight of sulfur dioxide was removed from the boiler (610) and subsequently fed to the absorber column (562).
[0101] The furnace (703) with burner (701) and duct (702) confines the components of the heat exchangers in advance of the water saturator (506) to the absorber outlet (562), as shown by the dotted outline.
[0102] The conditions and experimental results of these experiments are shown in table 6.



[0103] The concentration of sulfur dioxide in the absorption solution decreased from 3.68% by weight to 0.53% by weight, which represents an 84% recovery of sulfur dioxide in the extractor.
[0104] In view of the above information, it will be noted that the various objectives of the invention are accomplished and other advantageous results achieved.
[0105] The various changes could be made to the above processes without departing from the scope of the invention, it is intended that all material contained in the above description and shown in the accompanying Figures is to be interpreted as illustrative and not in a limiting sense.
[0106] By introducing elements of the present invention or the preferred embodiment(s) thereof, the articles "one", "one (1)", "one", "one (1)", "O". “a”, “said” and “said” are intended to mean that there is one or more of the elements. The terms "comprise", "include" and "have" are intended to be inclusive and mean that there may be additional elements in addition to the elements listed.

权利要求:
Claims (9)
[0001]
1. PROCESS TO REMOVE AND RECOVER SULFUR DIOXIDE, selectively from an effluent gas (10) that contains sulfur dioxide and oxygen, which comprises: placing the effluent gas (10) in contact with an aqueous buffered absorption solution in a sulfur dioxide absorber (11), which thereby absorbs sulfur dioxide from the effluent gas (10) in the absorption solution and produces an exhaust gas (18), from which sulfur dioxide has been removed, and an absorption solution enriched with sulfur dioxide (16); heating the absorption solution enriched with sulfur dioxide (16) in a sulfur dioxide extractor (20) to desorb sulfur dioxide and thereby produce a solution of absorbing regenerated sulfur dioxide (14) and an extractant gas enriched with sulfur dioxide (23); and reintroduce the regenerated sulfur dioxide absorber (14) to the sulfur dioxide absorber (11), characterized in that the buffered aqueous absorption solution comprises sodium malate, in which the carboxylic group with a pKa of 3.4 is completely neutralized and the carboxylic group with a pKa of 5.11 at 25°C is neutralized to within 20% of the equivalence point, and wherein the aqueous buffered absorption solution comprises an oxidation inhibitor selected from the group consisting of ascorbic acid , ethylenediaminetetraacetic acid, p-phenylenediamine, hydroquinone and mixtures thereof.
[0002]
Process according to claim 1, characterized in that it further comprises recovering sulfur dioxide from the aqueous absorption solution enriched with sulfur dioxide (16), in which immediately after the step of heating the absorption solution enriched with sulfur dioxide sulfur (16) in the sulfur dioxide extractor (20) which produces a regenerated sulfur dioxide absorption solution (14) and an extractant gas enriched with sulfur dioxide (23) comprising water vapor and, before reintroduction from the regenerated sulfur dioxide absorber (14) to the sulfur dioxide absorber (11), the process further comprises: cooling the sulfur dioxide enriched extractant gas (23) in an upper high temperature condenser (40) of the sulfur dioxide extractor (20) to condense water vapor and produce a high temperature upper condenser gas effluent (42) comprising sulfur dioxide and water vapor and a condensate aqueous (44) comprising sulfur dioxide; heating the regenerated sulfur dioxide absorbing solution (14) in a reboiler (46) of the sulfur dioxide extractor (20), wherein the upper high temperature condenser (40) comprises a heat pump system evaporator in which a refrigerant is evaporated by heat transfer from the extractant gas enriched with sulfur dioxide (23) and the reboiler (46) of the sulfur dioxide extractor (20) comprises a system condenser. heat pump in which the refrigerant is condensed by heat transfer to the regenerated sulfur dioxide absorbing solution (14) and in which the regenerated sulfur dioxide absorbing solution (14) is heated to a temperature below 20 °C in excess of the temperature of the aqueous condensate (44); heat the aqueous condensate (44) from the upper high temperature condenser (40) in a condensate extractor (50) to desorb sulfur dioxide and produce an extra gas. condensate actor (53) comprising water vapor and sulfur dioxide desorbed from the aqueous condensate (44); and cool the condensate extractor gas (53) and high temperature upper condenser effluent gas (42) in a low temperature condenser (54) to condense water vapor and produce a stream of recovered sulfur dioxide (56) comprising sulfur dioxide obtained in the aqueous condensate (44) and the high temperature upper condenser gas effluent (42) and an extracted condensate effluent (58) emptied of sulfur dioxide.
[0003]
Process according to claim 1, characterized in that it further comprises recovering sulfur dioxide from the aqueous absorption solution enriched with sulfur dioxide (16), in which immediately after the step of heating the absorption solution enriched with sulfur dioxide sulfur (16) in the sulfur dioxide extractor (20) which produces a regenerated sulfur dioxide absorption solution (14) and an extractant gas enriched with sulfur dioxide (23) comprising water vapor and, before reintroduction of the regenerated sulfur dioxide absorbing solution (14) to the sulfur dioxide absorbent (11), the process further comprises: increasing the pressure of the extractant gas enriched with sulfur dioxide (23); cooling the extractant gas enriched with sulfur dioxide pressurized (61) by means of heat transfer to the regenerated sulfur dioxide absorbing solution (14) in a reboiler (46) of the sulfur dioxide extractor (20) to condense steam from water and produce a boiler gas effluent (62) comprising sulfur dioxide and water vapor and an aqueous condensate (64) comprising sulfur dioxide; heat the aqueous condensate (64) from the reboiler (46) in a condensate extractor (50) to desorb sulfur dioxide and produce a condensate extractor gas (53) comprising water vapor and sulfur dioxide desorbed from the aqueous condensate (64); and cool the condensate extractor gas (53) and reboiler gas effluent (62) in a low temperature condenser (54) to condense water vapor and produce a recovered sulfur dioxide stream (56) comprising sulfur dioxide obtained in the aqueous condensate (64) and the reboiler gas effluent (62) and an extracted condensate effluent (58) emptied of sulfur dioxide.
[0004]
Process according to claim 1, characterized in that the absorption solution enriched with sulfur dioxide (16) is heated by heat transfer from the effluent gas (10) and/or the regenerated sulfur dioxide absorption solution (14 ) without the addition of external heat.
[0005]
5. Process, according to claim 4, characterized in that the temperature of the effluent gas (10) is not reduced below 50°C.
[0006]
Process according to claim 1, characterized in that the absorption solution enriched with sulfur dioxide (16) is heated by heat transfer from the effluent gas (10) and/or the regenerated sulfur dioxide absorption solution (14 ) and the temperature difference between the absorption solution enriched with sulfur dioxide (16) introduced to the extractor (20) and the regenerated absorption solution (14) is less than 40°C.
[0007]
Process according to claim 1, characterized in that it further comprises, before reintroducing the regenerated sulfur dioxide absorption solution (14) to the sulfur dioxide absorber (11), treating an air stream (30) of the regenerated sulfur dioxide absorption solution (14) wherein the treatment process comprises: diverting at least a portion of the regenerated absorption solution (14) exiting the extractor (20) as a stream of air (30); air stream water (30) of the regenerated sulfur dioxide absorption solution (14) at a temperature of at least 40°C to produce a concentrated absorption solution (34) supersaturated in the sulfate salt; precipitating the salt crystals of sulfate from the concentrated absorption solution (34) to form a crystallization slurry comprising precipitated sulfate salt crystals and a mother liquor; separating the sulfate salt crystals from the mother liquor to form a treated absorption solution comprising the malic acid salt; and combine the treated absorption solution with the remainder of the regenerated absorption solution (14), which is reintroduced to the sulfur dioxide absorbent (11).
[0008]
Process according to claim 7, characterized in that water is evaporated from the air stream (30) of the regenerated sulfur dioxide absorption solution (14) at a temperature of at least 60°C.
[0009]
Process according to any one of claims 7 to 8, characterized in that the sulfate salt crystals precipitated from the concentrated absorption solution (34) comprise sodium sulfate crystals, and the water is evaporated from the absorption solution (34 ) under conditions to inhibit the formation and precipitation of sodium sulfate decahydrate.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2031802A|1932-05-06|1936-02-25|Ici Ltd|Recovery of sulphur dioxide from gas mixtures|

---

US2729543A|1950-12-12|1956-01-03|Union Oil Co|Removal of sulfur dioxide from gases containing the same|

---

US3653812A|1969-07-18|1972-04-04|Wellman Lord Inc|Process for removal of sulfur dioxide from gas streams|

---

US3833508A|1971-04-27|1974-09-03|Itt|Gas removal method and composition|

---

JPS5017439B2|1971-11-02|1975-06-20|

---

US3970744A|1974-11-07|1976-07-20|Ralph M. Parsons Company|Process for the production of sulfur from sulfur dioxide extracted from gas streams|

---

JPS544934B2|1975-06-24|1979-03-12|

---

DE2623963A1|1976-05-28|1977-12-08|Bayer Ag|Sulphur dioxide removal from residual gases - by absorbing with a buffered aq. soln. of organic acids|

---

US4133650A|1976-05-28|1979-01-09|Bayer Aktiengesellschaft|Removing sulfur dioxide from exhaust air|

---

US4083944A|1976-12-17|1978-04-11|Arthur G. Mckee & Company|Regenerative process for flue gas desulfurization|

---

JPS53106382A|1977-02-28|1978-09-16|Chiyoda Chem Eng & Constr Co Ltd|Simultaneous desulfurization and denitration method for exhaust gas|

---

US4140751A|1977-03-04|1979-02-20|Peabody Process Systems, Inc.|Process for pressure stripping of sulfur dioxide from buffered solutions|

---

CA1106576A|1977-03-25|1981-08-11|Alexander J. Kosseim|Process for removing so.sub.2 from effluent gases and for removing heat stable salts from systems in which they accumulate using an anion exchange resin|

---

SE405109B|1977-04-12|1978-11-20|Svenska Flaektfabriken Ab|PROCEDURE FOR EXTRACTING CONCENTRATED SULFUR DIOXIDE FROM EXHAUST SULFUR DIOXIDE|

---

UST970008I4|1977-05-05|1978-05-02|Tennessee Valley Authority|Removal and recovery of sulfur oxides from gas streams with melamine|

---

US4222991A|1978-05-18|1980-09-16|Union Oil Company Of California|Process for removing SOx and NOx compounds from gas streams|

---

US4255400A|1978-07-03|1981-03-10|New World Business Corporation|Process for oxidizing oxides of sulfur|

---

SE429200B|1978-10-31|1983-08-22|Flaekt Ab|PROCEDURE FOR RECOVERY OF SODIUM CITRATE FROM WATER SOLUTIONS USED IN AN ABSORPTION / DRIVING PROCEDURE FOR SO? 712 RECOVERY|

---

US4432962A|1979-06-20|1984-02-21|Union Oil Company Of California|Method for removing hydrogen sulfide from gas streams|

---

US4366134A|1979-11-14|1982-12-28|Pfizer Inc.|Flue gas desulfurization process|

---

BR8205991A|1982-09-30|1984-05-08|Ultrafertil Sa|SULFUR BORING PROCESS|

---

US4444571A|1983-03-07|1984-04-24|Bend Research, Inc.|Energy-efficient process for the stripping of gases from liquids|

---

US4576813A|1983-07-05|1986-03-18|Monsanto Company|Heat recovery from concentrated sulfuric acid|

---

US4996038A|1983-07-05|1991-02-26|Monsanto Company|Heat recovery from concentrated sulfuric acid|

---

US4695349A|1984-03-07|1987-09-22|Linde Aktiengesellschaft|Process and apparatus for distillation and/or stripping|

---

US4670242A|1984-11-09|1987-06-02|Monsanto Company|Heat recovery from concentrated sulfuric acid|

---

US5068419A|1986-12-18|1991-11-26|Uop|Separation of an organic acid from a fermentation broth with an anionic polymeric adsorbent|

---

NO164218C|1988-02-24|1990-09-12|Sintef|PROCEDURE FOR CLEANING AFFICIENT BUFFER SOLUTIONS.|

---

US5130112A|1990-03-23|1992-07-14|Monsanto Company|Method for recovering high grade process energy from a contact sulfuric acid process|

---

US5447575A|1991-05-31|1995-09-05|The Dow Chemical Company|Degradable chelants having sulfonate groups, uses and compositions thereof|

---

RU2050314C1|1991-12-29|1995-12-20|Всероссийский научно-исследовательский институт газа и газовых технологий|Absorbent for gas scrubbing from hydrogen sulfide|

---

US5622681A|1992-01-21|1997-04-22|The Dow Chemical Company|Dialysis separation of heat stable organic amine salts in an acid gas absorption process|

---

US5292407A|1992-12-18|1994-03-08|Union Carbide Chemicals & Plastics Technology Corporation|Process for converting heat stable amine salts to heat regenerable amine salts|

---

US5450728A|1993-11-30|1995-09-19|Air Products And Chemicals, Inc.|Recovery of volatile organic compounds from gas streams|

---

US5538707A|1994-03-01|1996-07-23|Monsanto Company|Acid concentration control in SO3 absorption|

---

US5569443A|1994-11-18|1996-10-29|The Dow Chemical Company|Method for removing hydrogen sulfide from a gas using polyamino disuccinic acid|

---

US5582020A|1994-11-23|1996-12-10|Mainstream Engineering Corporation|Chemical/mechanical system and method using two-phase/two-component compression heat pump|

---

BR9606947A|1995-02-06|1997-12-23|Biostar Bv|Process and device for purifying flue gas|

---

US5785888A|1995-03-24|1998-07-28|Milmac Operating Company|Method for removal of sulfur dioxide|

---

NO312131B1|2000-03-06|2002-03-25|Olav Erga|Process for removing sodium sulfate from a phosphate solution|

---

GB0021409D0|2000-08-31|2000-10-18|Boc Group Plc|Treatment of a gas stream containing hydrogen sulphide|

---

US7056482B2|2003-06-12|2006-06-06|Cansolv Technologies Inc.|Method for recovery of CO2 from gas streams|

---

US7214358B2|2003-08-13|2007-05-08|Cansolv Technologies Inc.|Low energy regenerable SO2 scrubbing process|

---

DE102004011427A1|2004-03-09|2005-09-29|Basf Ag|Absorbent with improved oxidation resistance and process for deacidifying fluid streams|

---

US20080044333A1|2004-07-30|2008-02-21|Hakka Leo E|Method and apparatus for NOx and Hg removal|

---

JP4344668B2|2004-09-21|2009-10-14|株式会社伊藤園|Method for removing nitric acid from aqueous liquid and method for producing beverage|

---

US7708804B2|2007-07-11|2010-05-04|L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|Process and apparatus for the separation of a gaseous mixture|

---

WO2009065218A1|2007-11-20|2009-05-28|The University Of Regina|Method for inhibiting amine degradation during co2 capture from a gas stream|

---

US8063112B2|2008-12-08|2011-11-22|Cansolv Technologies Inc.|Process for the regeneration of an ion exchange resin using sulfurous acid|

---

CN101481095A|2009-02-05|2009-07-15|中国石化集团南京设计院|Process for recovering and utilizing sulfuric acid manufacture energy|

---

CN101869824B|2009-04-21|2012-06-06|攀钢集团攀枝花钢铁研究院有限公司|Flue gas desulfurizing agent and flue gas desulfurization method|

---

AU2010330659A1|2009-12-09|2012-07-26|University Of Regina|Alcohol-based gas stripping process|

---

US8283259B2|2010-08-31|2012-10-09|Micron Technology, Inc.|Methods of removing a metal nitride material|

---

CN102659568B|2012-05-03|2015-03-18|中粮生物化学（安徽）股份有限公司|Method for continuously removing cations out of solution containing citric acid|EP2696970A4|2011-04-11|2014-09-03|Electrosep Technologies Inc|Process for purifying absorbents comprising polyethylene glycol dimethyl ethers|

---

ES2821501T3|2012-05-02|2021-04-26|Mecs Inc|Regenerative recovery of effluent gas pollutants|

---

CN102716667B|2012-07-10|2015-02-25|中国华电工程有限公司|Ammonia regeneration method and device for activated coke|

---

DE102012017045A1|2012-08-29|2014-05-15|Thyssenkrupp Uhde Gmbh|Process for washing sulfur-containing gases with a circulating ammonia-containing washing solution|

---

KR102248675B1|2013-03-15|2021-05-07|엠이씨에스, 인코포레이티드|Recovery of sulfur trioxide heat of absorption|

---

CA2902732C|2013-03-15|2021-10-26|Mecs, Inc.|Regenerative recovery of contaminants from effluent gases|

---

CN103432882B|2013-07-09|2016-08-10|南京信息工程大学|A kind of separate the absorbent of sulfur dioxide in gaseous mixture|

---

KR101495876B1|2013-12-10|2015-02-26|한국과학기술연구원|Tertiary amine-based sulfur dioxide absorbent containing nitrile functional group|

---

CN103611391B|2013-12-12|2016-01-20|北京博源恒升高科技有限公司|Glycols composite solution removes the method for SOx in gas|

---

CN103623689B|2013-12-12|2016-06-29|北京博源恒升高科技有限公司|The method of SOx in polyhydric alcohol composite solution elimination gas|

---

CN105413399A|2015-11-27|2016-03-23|攀钢集团攀枝花钢铁研究院有限公司|Simultaneous desulphurization and denitration system and process thereof|

---

US10543453B2|2016-04-18|2020-01-28|Mecs, Inc.|Removal of sulfate from solvent solutions using an anion exchange resin|

---

CN106276812B|2016-09-14|2019-07-12|北京清新环境技术股份有限公司|A kind of high temperature sulphur-containing exhaust gas prepares liquid sulfur dioxide device|

---

CN109553075A|2017-06-21|2019-04-02|山东康宝生化科技有限公司|A kind of Sucralose exhaust gas processing device|

---

US11000803B2|2018-01-16|2021-05-11|Nuorganics LLC|Systems and methods for concentrating a substance recovered from a gas stream|

---

KR102234106B1|2019-07-16|2021-04-01|한국에너지기술연구원|Absorbent, composition and method for simultaneous removal of nox and sox|

---

FR3106063A1|2020-01-10|2021-07-16|Prevor International|Corrosive gas chemical decontamination system|

法律状态:
2020-09-15| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-09-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-02-02| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US40842010P| true| 2010-10-29|2010-10-29|

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US61/408,420|2010-10-29|

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PCT/US2011/058314|WO2012058558A2|2010-10-29|2011-10-28|Regenerative recovery of sulfur dioxide from effluent gases|

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