Abstract:
The invention proposes a method of destruction of volatile organic and inorganic compounds in wastewater, this method includes following stages: stripping the aforementioned volatile compounds in a stripping-chemisorption column; preliminary heating the gaseous medium containing these volatile compounds in a first heat regenerator; thermal, flare or thermo-catalytic oxidation of the volatile compounds in circulating gaseous medium; cooling the gaseous medium in a second heat regenerator; chemisorption of acidic gases from the gaseous medium in the stripping-chemisorption column with stripping at the same time additional amount of the volatile compounds from the wastewater. After specific period, direction of the gaseous medium flow is alternated. The proposed method can be executed at elevated temperature. The invention includes as well systems realizing the proposed method.

Description:
CROSS-REFERENCE APPLICATION 
     Not Applicable 
     FEDERALLY SPONSERED RESEARCH OF DEVELOPMENT 
     Not Applicable 
     BACKGROUND OF THE INVENTION 
     The problem of treatment of wastewater contaminated with volatile organic or inorganic compounds becomes very pressing for many facilities and for many branches of industry. In some cases, volatile organic and inorganic compounds present a major contributor to overall pollution in a facility. 
     There are different methods of volatile organic and inorganic compounds control in wastewater. 
     Detailed review of these methods is presented in the article: Victor H. Edwards “VOC-Control Options During Wastewater Treatment” CHEMICAL ENGINEERING, September 2000, pp. 105÷108. 
     According to this article, all methods of control of volatile organic and inorganic compounds in wastewater can be classified under two main types: 1) with transfer of volatile organic and inorganic compounds from wastewater into vapor phase by distillation, air stripping, steam stripping, inert-gas stripping, fuel-gas stripping, vacuum distillation and vacuum stripping; 2) with transfer of volatile organic and inorganic compounds into a liquid or solid phase: solvent extraction, liquid ion exchange, reverse osmosis, adsorption, ion exchange and precipitation. 
     Each aforementioned method is distinguished by its advantages and drawbacks. 
     In the case of application of air stripping related to the first group, this method should be combined with an additional method for treating air laden with volatile organic and inorganic compounds. There are several physicochemical methods of such additional treatment: flare, feed to a furnace or boiler, feed in a thermal or catalytic incinerator, condensation, cryogenic condensation, adsorption using activated carbon, alumina or zeolites. 
     Each of these additional methods has in turn several advantages and disadvantage related to its cost, efficiency, reliability and safety. As it is known from technical literature (see, for example, “THERMAL AND THERMO-CATALYTIC TREATMENT OF WASTE GASES” Naukova Dumka, 1984, pp. 17÷22 (in Russian)), thermal method of oxidation of waste gases requires about of 26÷45 kg of liquid fuel per 1000 m 3  of waste gases and the thermo-catalytic method −15÷25 kg of liquid fuel correspondingly. It is clear, that higher concentration of volatile organic and inorganic compounds in the volatile organic and inorganic compounds-laden air after the air stripping process causes diminishment of a liquid or gaseous fuel required for thermal or thermo-catalytic oxidation of volatile organic and inorganic compounds presented in the wastewater. 
     In order to achieve higher concentration of volatile organic and inorganic compounds in the volatile organic and inorganic compounds-laden air it is possible to perform the air stripping process with a stage of previous heating wastewater in a heat exchanging unit, it allows achieving higher concentration of volatile organic and inorganic compounds in air after stripping process and, on the other hand, to treat wastewater containing volatile organic compounds with relatively high temperature of boiling at the atmospheric pressure. 
     In addition, the rate of stripping at elevated temperature is substantially higher, i.e. for the same size of an air-stripping tower, it is possible to treat greater amount of wastewater in the same period. 
     However, the common process of air stripping at elevated temperature is characterized by great heat losses at the expense of enhanced water evaporation into the volatile organic and inorganic compounds-laden air. As a result, energy cost for wastewater treatment by air stripping at elevated temperatures is very high. 
     BRIEF SUMMARY OF THE INVENTION 
     A proposed technical solution is based on the stripping-chemisorption process performed mainly at elevated temperature. 
     A system of treatment of volatile organic and inorganic compounds contained in wastewater comprises some main units: a tank filled with the wastewater; two stripping-chemisorption columns installed on the tank through two connecting branches; two fans or blowers causing circulation of the gaseous medium through the system with periodical alternation of circulation direction; two heat regenerators that operate in opposite phases with periodical alternation their modes; a unit of thermal, flare or thermo-catalytic oxidation of volatile organic and inorganic substances contained in the circulating gaseous medium. 
     The wastewater in tank has alkali reaction (pH &gt;7); it can be achieved by addition of alkali substances into the wastewater. This serves for chemisorption of acidic gases obtained by thermal, flare or thermo-catalytic oxidation of the organic or/and inorganic compounds evaporated previously in the stripping-chemisorption columns. The system is provided with an inlet connection for oxygen delivery and with an outlet connection for blowing out the system, especially, at the initial stage of its operation. 
     The unit of thermal, flare or thermo-catalytic oxidation (incineration) of volatile organic and inorganic compounds contained in the gaseous medium can be designed in flare, thermal or thermo-catalytic forms. 
     A circulation pump associated with the tank performs supply of the wastewater from this tank to the upper section(s) of the stripping-chemisorption column(s), which are installed on the tank through the aforementioned connecting branches. 
     The upper edges of the stripping-chemisorption columns are joined in turn with the bottoms of fixed packed beds (heat regenerators) serving for periodic accumulation of heat from the gaseous medium after flare, thermal or thermo-catalytic oxidation of volatile organic and inorganic compounds contained in this gaseous medium and its preheating before their flare, thermal or thermo-catalytic oxidation. The upper edges of these fixed packed beds (heat regenerators) are communicating with a unit of flare, thermal or thermo-catalytic oxidation. 
     Besides, in the case of thermo-catalytic oxidation, there are two modules of ultimate heating situated between the unit of flare, thermal or thermo-catalytic oxidation and the heat regenerators. 
     Both connecting branches, which are installed on the tank, are joined by two parallel channels, which are provided with demisters and shutters installed in their extreme sections; the fans are installed in these channels and actuated alternatively in accordance with modes of the heat regenerators, they cause circulation of the gaseous medium through the entire system. The basic processes in the entire system include: stripping-chemisorption by the stripping-chemisorption columns, preheating the gaseous medium by one of the heat regenerators, thermal, flare or thermo-catalytic oxidation in the thermal or thermo-catalytic oxidation unit, and heat accumulation in the other heat regenerator. 
     There are two tubular branches inserting from the lower edges of the connecting branches into the wastewater in the tank, it allows to prevent bypass flow of the gaseous medium via the upper space of the tank (if this tank is not filled completely with the wastewater). 
     In the case of thermal oxidation of volatile organic and inorganic compounds in the circulating gaseous medium, it is possible to design the heat regenerators and the thermal oxidation unit as a combined module in the form of a tube from refractory material with an internal packing; the middle section of the tube is provided with a heating means (electrical or flare) and the extreme sections of this refractory tube with the internal packing serve as the heat regenerators. 
     In another version, the fans are installed between the stripping-chemisorption column and the heat regenerators. In this version, the stripping-chemisorption columns are installed directly on the tank with wastewater (without application of the connecting branches) and the aforementioned tubular branches inserted in the space of the wastewater tank are not applied. The upper internal section of the tank, which is not filled with the wastewater, serves in this case for circulation of the gaseous medium and the aforementioned parallel channels are not applied as well. 
     The tank can be provided with a build-in or external heat-exchanging module. 
     In addition, the proposed system is provided with proper control equipment and valves. 
     The proposed system, when it is designed for thermo-catalytic oxidation of volatile organic and inorganic compounds, operates in the following manner:
         the tank should be filled with wastewater contaminated with volatile organic and inorganic compounds;   if it is necessary, the wastewater temperature in the tanks is established at a level, which is required for rapid and safety stripping volatile organic and inorganic compounds with their following oxidation in gaseous medium;   alkalinity of this wastewater in the tanks can be established previously or in the process of oxidation of volatile organic and inorganic compounds at a level, which ensures complete neutralization and chemisorption of acidic gases obtained as the result of oxidation of these volatile organic and inorganic compounds;   the circulation pump is actuated and it supplies the wastewater from the tank into one or both stripping-chemisorption columns; if it is necessary, the wastewater temperature in this tank is established by its heat-exchanging module;   at the same time, one of fans is actuated in such a way, that it causes circulation of the gaseous medium in the entire system when this gaseous medium flows co-currently or counter-currently regarding the wastewater flow in the operating stripping-chemisorption columns;   after preheating the gaseous medium in one fixed packed bed (heat regenerator) and its ultimate heating by the electrical heater in the module of ultimate heating the gaseous medium passes through the catalytic bed, and volatile organic and inorganic compounds contained in the gaseous medium are oxidized by oxygen presented in the gaseous medium;   then the gaseous medium is pre-cooled in the opposite heat regenerator;   oxygen or air is steadily supplied into the gaseous medium in accordance with amount of oxygen which is run out for oxidation of volatile organic and inorganic compounds in the gaseous medium.       

     Finally cooling is performed in the following operating stripping-chemisorption column(s) itself. Besides, this operating stripping-chemisorption column provides additional evaporated portions of volatile organic and inorganic compounds into the circulating gaseous medium, causes absorption of the oxidation products in the wastewater and regulates the water vapors&#39; content in the gaseous medium. 
     As the average temperature in the heat regenerator, which serves at this point for cooling the gaseous medium after the unit of thermo-catalytic oxidation, is elevated up to a certain level, operation of the fans is alternated, i.e. the first fan will be in its idle state and the second fan begins to circulate the gaseous medium through the system in opposite direction. As this takes place, the second module of ultimate heating is actuated instead of the first module. 
     After getting sufficiently low concentration of volatile organic and inorganic compounds in the wastewater, the process is finished and the wastewater is discharged from the tank. 
     In order to indicate temperature change and volatile organic and inorganic compounds&#39; concentration in the wastewater or in the gaseous medium, the system is provided with a proper monitoring unit. 
     It is possible to simplify the system described above by introduction of four shutoff dampers. In this case, there is only one stripping-chemisorption column. Closing and opening the diagonally positioned pairs of the shutoff dampers can alternate direction of the gaseous medium flow via the aforementioned fixed packed beds. 
     Two modules of ultimate heating and one module of thermo-catalytic oxidation are positioned between these fixed packed beds (heat regenerators), the modules of ultimate heating are energized alternatively in accordance with direction of the gaseous stream. This version gives possibility to apply only one fan. 
     If wastewater contains volatile organic acid, for example—acetic acid, than stripping and chemosorption processes should be performed in different columns connected in series, because high alkalinity may significantly diminish volatility of this acid. In this case chemisorption of the gases obtained by thermo-oxidation or thermo-catalytic oxidation is performed in a separate column by alkaline solution. 
     The stripping-chemisorption columns can be of the spray or packed types. 
     In the case of flare or thermal oxidation, the modules of ultimate heating are not applied. 
     The heat exchanging module(s) of the tank(s) allows to change temperature of the wastewater in the tank in order to establish sufficiently high rate of evaporation of volatile organic and inorganic compounds and, on the other hand, to prevent danger of explosion of the gaseous medium. 
     In the case of flare or thermal oxidation of volatile organic and inorganic compound-laden gaseous medium there is only one module of ultimate heating (or incineration) and oxidation is performed in this module. 
     The proposed design of the stripping-chemisorption-oxidation system allows diminishing consumption of electrical energy, liquid or gaseous fuel for flare, thermal or thermo-catalytic oxidation of volatile organic and inorganic compounds contained in wastewater. This diminishment can be estimated by a factor of 2÷4. 
     In the case, when the wastewater contains high concentration of volatile organic and inorganic compounds, it is possible to diminish further this energy expenditure at the cost of the heat released in the process of volatile organic and inorganic compound oxidation. 
     In the batch version of the process, the temperature of the wastewater is changed during the process of stripping-chemisorption in such a way, that concentration of explosive volatile organic and inorganic compounds in the gaseous medium in the system is significantly lower than a dangerous level, which can cause explosion. In addition, it is possible to cool the wastewater in the tanks at the early stage of oxidation in order to prevent danger of explosion (in the case of high initial concentration of volatile organic and inorganic compounds in the wastewater). 
     In the continuous version of the process, there are some stripping-chemisorption-oxidation sub-units, which are arranged in line and the temperature of the wastewater is gradually elevated in the direction from the first stripping-chemisorption-oxidation sub-unit to the latter. In such a way, concentration of volatile organic and inorganic compounds in the gaseous medium of each stripping-chemisorption-oxidation sub-unit is lower than the dangerous level because gradually diminishment of volatile organic and inorganic compound concentration in the stripping-chemisorption-oxidation sub-units according to downstream of the wastewater. 
     The main area of application of the proposed systems is treatment of wastewaters of different facilities. 
     However, these systems can be used as well for treatment of groundwater in the case, when this groundwater has high level of contamination by volatile organic and inorganic compounds (for example, in the case of spillage at a facility). 
     In addition the proposed system can be used for incineration of water-insoluble organic liquids, for example, waste PCB. In this case, the tank(s) of the system is filled with the waste organic liquid and aqueous alkali solution in a required proportion. The tank is provided with a mixer, which generates emulsion of both components (the aqueous alkali solution and the organic liquid), this emulsion is supplied by the circulation pump to the stripping-chemisorption column. 
    
    
     
       BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS 
         FIG. 1  is a general scheme of a system for destruction of volatile organic and inorganic compounds contained in wastewater, this scheme includes a tank with a circulating pump and two stripping-chemisorption columns; oxidation of volatile organic and inorganic compounds is performed by a thermo-catalytic unit. 
         FIG. 2  is a general scheme of a system for destruction of volatile organic and inorganic compounds contained in wastewater, this system includes a tank with a circulating pump and two stripping-chemisorption columns, oxidation of volatile organic and inorganic compounds is performed by a thermal unit. 
         FIG. 3  is a general scheme of a system for destruction of volatile organic and inorganic compounds contained in wastewater, this system is based on thermal oxidation of volatile organic and inorganic compounds; the heat regenerators and the thermal oxidation unit are designed as one combined module. 
         FIG. 4  is a general scheme of a system for destruction of volatile organic and inorganic compounds contained in wastewater by thermo-catalytic oxidation; this system comprises one stripping-chemisorption column and one fan. 
         FIG. 5  is a general scheme of a system for destruction of organic acids contained in a wastewater. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       FIG. 1  shows a general scheme of a batch system for destruction of volatile organic and inorganic compounds contained in wastewater by thermo-catalytic oxidation. 
     This scheme includes tank  101  filled with wastewater  102  in such a way, that there is a free upper space intended for circulation of the gaseous medium. The tank comprises: outlet connections  104  and  103 , an inlet connection  105 , flanges  106  and  107  for installation of stripping-chemisorption columns  110  and  112 , a built-in heat exchanging module  109 . This heat exchanging module is installed on an additional flange  111 . The stripping-chemisorption columns  110  and  112  comprise packings  113  and  114 , distributors  115  and  131 , demisters  117  and  116 . A circulation pump  108  performs circulation the wastewater via the stripping-chemisorption columns  110  and  112 . Fans  118  and  119  are installed on the upper flanges of the stripping-chemisorption columns  110  and  112 . 
     In addition, there are two heat regenerators  120  and  121  installed by their lower flanges on fans  118  and  119 . The heat regenerator  120  is provided with an inlet connection  129  for oxygen delivery and the heat regenerator  121 —with an outlet connection  130  for purging the entire system. 
     The heat regenerator  120  is filled with packing  122 , and heat regenerator  121 —with packing  123 . 
     Module  124  for thermo-catalytic oxidation consists of two sub-modules  125  and  126  of ultimate heating, and a catalytic packed bed  127 . 
     The heat regenerators  120 ,  121  and module  124  are provided with a thermal insulation  128 . 
       FIG. 2  shows a general scheme of a batch system for destruction of volatile organic and inorganic compounds contained in wastewater by thermal oxidation. This scheme includes tank  201  filled with wastewater  202 . Tank  201  is provided with an inlet connection  204 , outlet connections  203  and  204 , flanges  206  and  207  for installation of two connecting branches  212  and  213 . Each connecting branch is provided with two lateral tees. 
     In addition, tank  201  is provided with a built-in heat exchanging module  208 . Tubular branches  209  and  210  are installed on flanges  206  and  207 . They are immersed into the wastewater; it prevents bypass flow of the gaseous medium through the upper space of the tank. 
     The connecting branch  212  is provided with an inlet connection  240  for oxygen delivery, and the connecting branch  213 —with an outlet connection  241  for purging the entire system. The lateral tees of the connecting branches are joined by two joints; there are demisters  214  and  215 , fans  217  and  219 , back draft shutters  216  and  218 , which are installed in these joints. 
     The upper flanges of the connecting branches  212  and  213  serve for installation of two stripping-chemisorption columns  220  and  221  with supporting grids  222  and  223 , and packings  224  and  225 . 
     In addition, there are distributors  226 ,  229  and demisters  228 ,  227  installed in the stripping-chemisorption columns. Pump  211  performs supply of the wastewater into the stripping-chemisorption columns. 
     The upper flanges of the stripping-chemisorption columns serve for installation of their associated heat regenerators  233 ,  232  with packings  238  and  242 . This installation is performed through two bellow joints  222  and  223 . 
     The low sections of the heat regenerators consist off metal branches  234  and  235 ; refractory tubes  236  and  237  are inserted into these metal branches. These refractory tubes are joined by refractory elbows  244  and  245  with module  243  of thermal oxidation; this module comprises a refractory tube  246  and an internal electrical heater  243 . 
     The heat regenerators  232 ,  233  and module  243  of thermal oxidation are provided with a thermal insulation  239 . 
       FIG. 3  shows a general scheme of a batch system for destruction of volatile organic and inorganic compounds contained in wastewater a plant of volatile organic and inorganic compound-control in wastewater, this scheme is based on thermal oxidation of volatile organic and inorganic compounds; the heat regenerators and the unit of thermal oxidation are designed as one combined module of tubular form. 
     This scheme includes tank  301  filled with wastewater  302 . Tank  301  is provided with an inlet connection  304 , outlet connections  303  and  307 , flanges  306  and  308  for installation two connecting branches  313  and  315 . Each connecting branch is provided with two lateral tees. 
     In addition, tank  301  is provided with a built-in heat exchanging module  305 . Tubular branches  337  and  338  are installed on flanges  306  and  308 . They are immersed into the wastewater, it prevents bypass flow of the gaseous medium through the upper space of the tank. 
     The connecting branch  315  is provided with an inlet connection  311  for oxygen delivery, and the connecting branch  313 —with an outlet connection  309  for purging the entire system. The lateral tees of the connecting branches are joined by two joints; there are demisters  316  and  317 , fans  312  and  320 , back draft shutters  314  and  321 , which are installed in these joints. 
     The upper flanges of the connecting branches  313  and  315  serve for installation of two stripping-chemisorption columns  318  and  319  with packings  323  and  322 . 
     In addition, there are distributors  325 ,  327  and demisters  326 ,  328  installed in the stripping-chemisorption columns. Pump  310  performs supply of the wastewater into the stripping-chemisorption columns. 
     The upper flange of the stripping-chemisorption column  315  serves for installation a bellow joint  331 , which in turn serves for installation of a combined module  324  of heat regeneration—thermal oxidation. 
     The low section of the combined module  324  consists off a metal branch  330  with supporting grid  329 ; a refractory tube  336  is inserted into this metal branch. The refractory tube  336  is filled with packing  332 . 
     The middle section of the refractory tube  336  is provided with an external electrical heater  333 , and its lower and upper sections serve as heat regenerators. The refractory tube  336  is provided with a thermal insulation  335 . 
     A gas duct  334  communicates the upper section of the combined module  324  with the upper flange of the stripping-chemisorption column  319 . 
       FIG. 4  shows a general scheme of a plant of volatile organic and inorganic compound-control in wastewater by thermo-catalytic oxidation with one stripping-chemisorption column. 
     This scheme includes tank  401  filled with wastewater  402 . The tank comprises: outlet connections  404  and  403 , an inlet connection  405 , flange  410  and a built-in heat exchanging module  406 . Flange  410  serves for installation of a connecting branch  409  with a lateral tee. 
     A stripping-chemisorption column  416  is installed on the upper flange of the connecting branch  409 , this column comprises packing  411  and distributor  412 . 
     A circulation pump  407  performs circulation the wastewater via the stripping-chemisorption column  416 . 
     The lateral tee of the connecting branch  409  is joined with the proximal edge of a gas duct  420 ; the distal edge of this gas duct is joined with the upper flange of the stripping-chemisorption column  416 . In such a way, these units—the gas duct  420 , the stripping-chemisorption column  416  and the connecting branch  409 —present a closed loop for circulation of gaseous medium. The proximal section of the gas duct is provided with demister  413  and fan  414 . 
     There is a first additional gas duct  421 , which communicates the proximal and distal sections of the gas duct  420 . A heat regenerator  419 , module  426  of sub-module  426  of ultimate heating, module  417  of thermo-catalytic oxidation, sub-module  418  of ultimate heating, and a heat regenerator  429  are installed in-line on a second additional gas duct  430  communicating the first additional gas duct  421  with the gas duct  420 . 
     Two pair of dampers  431 ,  425  and  423 ,  422  are installed on the gas duct  420  and the first additional gas duct  421  from both sides with respect to the second additional gas duct  430 . Alternative shutting and opening the diagonally situated dampers gives possibility to alternate periodically direction of the gaseous medium flow via the aforementioned sequence of the modules and sub-modules installed on the second additional gas duct. 
       FIG. 5  shows a general scheme of a system for destruction of organic acids contained in a wastewater. 
     This scheme includes tank  501  filled with wastewater  502 . The tank comprises: outlet connections  504  and  503 , an inlet connection  505 , flange  510  and a built-in heat exchanging module  506 . Flange  510  serves for installation of a connecting branch  509  with a lateral tee. 
     A stripping column  516  is installed on the upper flange of the connecting branch  509 , this column comprises packing  511  and distributor  512 . 
     A circulation pump  507  performs circulation the wastewater via the stripping column  516 . There is a second tank  513  filled with alkaline solution  514 . The tank comprises: outlet connections  517  and  518 , an inlet connection  519 , flange  520  and a built-in heat-exchanging module  521 . Flange  520  serves for installation of a connecting branch  522  with a lateral tee. 
     A chemisorption column  523  is installed on the upper flange of the connecting branch  522 , this column comprises packing  524  and distributor  525 . 
     A circulation pump  526  performs circulation the alkaline solution via the chemisorption column  523 . 
     The lateral tee of the connecting branch  509  is connected with the lateral tee of the connecting branch  522  by a gas duct  527 . 
     The inlet flange of fan  528  is installed on the upper flange of the stripping column  516 . 
     The upper flange of the chemisorption column  523  and the outlet flange of fan  528  are communicated by a gas duct  529  which is branched in two parallel gas ducts  530  and  531 . The parallel gas ducts include two T-pieces  532  and  533 . The central branches of these T-pieces are communicated via a gas duct  534 , which incorporates a first heat regenerating bed  535 , an electrical heater  536  and a second heat regenerating bed  537 ; these units are positioned sequentially. 
     The system is provided with an inlet connection  508  for supply of oxygen and/or other gases into the gaseous circuit of this system, and with an outlet connection  515  for blow-out of the excessive gases from the system. 
     Two pairs of dampers  538 ,  539  and  540 ,  541  are installed on the gas ducts  530  and  531  from the both sides of the central branches of T-pieces  532  and  533 . 
     Alternative shutting and opening the diagonally situated dampers gives possibility to alternate periodically direction of the gaseous medium flow via the aforementioned sequence of the heat regenerating beds and the electrical heater.