Patent Application
20140073718
The present invention relates to a process for removing volatile organic compounds (VOCs) from a liquid, such as a latex, using multiple membranes.
Latex paints often contain VOCs at levels that produce undesirable odors. These VOCs, typically ppm levels of low molecular weight ketones, alcohols, acetates, and aldehydes, are not essential for the paint's performance but are added to facilitate various steps in the paint's manufacture. Accordingly, paints free of these odor producing agents are desired.
Removal or “stripping” of trace amounts of low molecular weight organics can be accomplished by contacting a liquid containing VOCs with a gas, such as air, or nitrogen, or steam. The gas can be passed through a sparger to create large numbers of small bubbles dispersed within the liquid. The bubbles rise to the surface of the bulk liquid, carrying a portion of the VOCs with them. Other well-known methods for carrying out stripping operations involve contacting liquid and gas in a trayed or a packed stripping tower. In all of these devices, the organic compounds transfer from the liquid phase to the gas phase due to favorable liquid-vapor equilibrium partition ratios or relative volatilities.
Although these conventional stripping processes are widely used for treating aqueous streams, these techniques are not as efficient for removing VOCs from latexes. First, because latexes are stabilized by significant amounts of surfactant, sparging produces high volumes of foam during the stripping operation, thereby causing major problems in the processing and packaging of the finished latex. Second, there is a need for a more economical process that can increase interfacial area for mass transfer and thus reduce the size and cost of the stripping equipment. It would therefore be an advance in the art of VOC removal to find a way to reduce concentrations of VOCs in latex paints in a more efficient manner.
The present invention relates to a process comprising the steps of:
and, concomitant with the passing of the liquid stream across the first surfaces of the first and second membranes;
wherein the flow of the stripping gas is countercurrent with the flow of the liquid stream;
wherein a portion of the liquid is recirculated across the first surface of the first membrane or the first surface of the second membrane or both, and/or a portion of the stripping gas is recirculated across the second surface of the second membrane or the second surface of the first membrane or both.
The present invention addresses a need in the art by providing an efficient way of removing VOCs from a liquid such as a latex.
The present invention addresses a need in the art by providing a process comprising the steps of:
and, concomitant with the passing of the liquid stream across the first surfaces of the first and second membranes;
wherein the flow of the stripping gas is countercurrent with the flow of the liquid stream;
wherein a portion of the liquid is recirculated across the first surface of the first membrane or the first surface of the second membrane or both, and/or a portion of the stripping gas is recirculated across the second surface of the second membrane or the second surface of the first membrane or both.
The present invention relates to a process for removing VOCs from a liquid stream by way of multiple membranes, each of which are advantageously housed in modules, which membranes provide an efficient means of stripping VOCs from a liquid feed such as latex, surfactant-laden wastewater, or brine, with internal recycle of a stripping gas. The process of the present invention strips VOCs from the feed with minimal consumption of stripping gas, such as air or nitrogen or steam, for good economy of operation. The process minimizes stripping gas by using multi-stage countercurrent processing with multiple membrane modules and by recycling (recirculating) a portion of the stripping gas within the process. In one embodiment of the invention, stripping gas is recycled to boost the gas velocity within a given module to improve mass transfer efficiency, thereby further reducing the amount of stripping gas required to strip VOCs to a desired level. In another embodiment, the liquid feed is recycled to boost the liquid velocity within a module in order to improve mass transfer efficiency, thereby reducing the transfer area and module size to strip VOCs to a desired level.
The first and second membranes (and optionally more membranes), which may be the same or different, are characterized by being permeable to VOCs and impermeable to the liquid. In one aspect, each membrane is a nanoporous hydrophobic polymeric membrane characterized by pore diameters in the range of 1 nm to 1000 nm, preferably in the range of 1 nm to 100 nm. In this aspect, the polymer is sufficiently hydrophobic so that water does not readily wet the clean polymer membrane surface prior to use, that is, so that water tends to form spherical beads of water droplets rather than thin films on the surface of the polymer. Thus, the nanoporous membrane is sufficiently hydrophobic to inhibit transport of liquid water through the membrane by, for example, wicking or pressure driven transport of water into the membrane. Examples of hydrophobic materials suitable for the nanoporous membrane include polyethylene, polypropylene, ethylene-propylene copolymer, polyvinylidene fluoride, or polytetrafluoroethylene.
The membranes may also be nonporous but highly permeable to organic solutes that are to be removed. Materials suitable for this membrane include cellulose acetate and crosslinked polyvinylalcohol. The membranes can be all nanoporous or all nonporous and highly permeable to organic solutes or combinations thereof.
One or more of the membranes may also comprise a composite membrane, which is a thin nanoporous or nonporous film supported on the surface of a thicker support membrane that provides mechanical strength. This support membrane is preferably macroporous, with pore diameters typically in the range of 1000 nm to 10,000 nm, to facilitate transport to the discriminating film. The support membrane may be made of any polymer with the required mechanical strength, including hydrophobic and hydrophilic polymers.
The membranes are preferably provided in the form of modules, which are housings for the membrane, most commonly a hollow fiber membrane module, a plate and frame membrane module, a flat spiral wound membrane module, a shell and tube module (also known as a fiber bundle module), or a combination thereof. These modules are well known in the art.
Referring to
VOCs pass from the liquid through the first membrane (22) and are carried away from the first module (20) by a flowing stream of stripping gas, which is countercurrent to the liquid stream. The stripping gas is fed initially from an inlet (50) through the second membrane module (30) and then to the first membrane module (20) across a second surface (22b) of the first membrane (22). A part of the vapor stream containing the VOCs leaves the first module (20) and flows to the vapor outlet (60). A part of the vapor stream containing the VOCs may also be recirculated back to the inlet of the first module (20). The stripping gas, which is passed across the second surface (32b) of the second membrane (32), is preferably not recirculated through the second module (30) because this second module (30) is used as a polishing module to achieve very low residual VOC levels in the treated liquid. This vapor stream is advantageously treated to eliminate the VOC wastes using methods known in the art before releasing the vapor into the atmosphere.
As used herein, the terms “first” and “second,” in reference to membranes and modules, have different meanings depending on the number of membranes and modules used in the process of the present invention. For a 2-module system, the first module is the module proximal to the liquid stream inlet while the second module is the module proximal to the stripping gas inlet. For a system comprising three or more modules, the first module can be any module except the module closest to the inlet for the stripping gas while the second module can be any module except the module closest to the liquid stream inlet. Thus, one or more ancillary modules housing one or more ancillary membranes having first and second surfaces may be placed in series with the first and second modules. The liquid stream passes across the first surface or surfaces of the one or more ancillary membranes and may optionally be recirculated across any or all of the first surface or surfaces of the one or more ancillary membranes; similarly, the stripping gases pass across the second surface or surfaces of the one or more ancillary membranes and may optionally be recirculated across any or all of the second surface or surfaces of the one or more ancillary membranes.
The process of the present invention may also include a means for removing a portion of the VOC content from the VOC-laden stripping gas. For example, a pressure-swing adsorption (PSA) unit may be added to a gas-recycle loop to remove a portion of the organic content, thereby reducing the need to inject clean gas from an external source. Such a PSA unit is operated in a cyclical manner: for a dual-bed system using activated carbon adsorbent, one adsorbent bed removes VOCs from the stripping gas while the other bed is regenerated at reduced pressure, as disclosed in U.S. Pat. No. 4,857,084. A small amount of cleaned gas can be used as backpurge to flush the regenerating bed of organics. The organic-laden backpurge gas can then be cooled below the dew-point of the VOCs, thereby condensing the VOCs and removing a portion from the stripping process. The saturated backpurge gas can then be recycled to the inlet to the on-line adsorbent bed.
Other types of adsorption processes include adsorbing organics from the stripping gas onto a bed of activated carbon adsorbent, followed by thermally regenerating the bed using steam. The VOC-laden stripping gas also may be processed in a thermal or catalytic oxidizer to destroy the VOC content, and a portion of the treated gas may be recycled back to the modules. Such processes are well-known in the art.
Where the stripping gas, preferably steam, contains a relatively high concentration of hydrophobic VOCs, a portion of the VOC content may be isolated from the process by condensing the organic-laden steam, decanting an organic layer that forms in a condensate decanter vessel (separation vessel), and re-boiling the aqueous condensate layer that remains after decanting the organic layer. A variety of well-known heat exchangers and mechanical vapor recompression (heat pump) strategies may be used to reduce energy consumption.
The process of the present invention is capable of reducing the VOC content in a relatively high solids content latex to a level that eliminates or substantially eliminates odor from malodorous components, or reduces the level of toxic components to innocuous levels, cleanly and efficiently.
This process configuration advantageously allows for flow rates of liquid or gas or both to be adjusted and optimized within a first membrane module, independent of the overall gas-to-liquid ratio used for the process. This processing flexibility provides operation of the first module at optimal liquid and gas velocities for good mass transfer performance independent of the amount of stripping gas used to treat a given amount of liquid.
Process configurations include two or more membrane modules wherein liquid or stripping gas or both are recycled within one or more of the modules; however, stripping gas is preferably not recycled around the module proximal to the stripping gas inlet (i.e., the polishing module). The preferential avoidance of recycling stripping gas around the polishing module results in a reduction of VOCs to very low levels because the gas used for stripping is clean gas that has not been contaminated with organics from recycled gas. Thus, the invention uses recycle of liquid or gas or both for optimal mass transfer at relatively high VOC concentrations with minimal use of stripping gas; the combination of recycling and processing in a polishing module using only clean stripping gas results in very low residual VOCs in the treated liquid.
Varying the recycle rate at each module allows optimization of VOC removal overall. For a process with three or more membrane modules, the stripping gas recycle rates can be adjusted for each module—preferably, highest for the feed module where VOC concentrations are highest, somewhat lower recycle to the next module where VOC concentrations are lower, and zero recycle to the module proximal to the inlet for the stripping gas, where VOC concentrations are lowest. Liquid may be recycled at each module.
The following example is for illustrative purpose only and is not intended to limit the scope of the invention.
The following example demonstrates extraction optimization using a 2-stage membrane setup as shown in
To lower the outlet VOC concentration, the recycle flow rate was increased but the net flow rate through each module was kept the same. For this example, enough latex was recycled to achieve a total flow rate to the module of 0.06 mL/s (0.04 mL/s recycle flow rate), which was the flow rate at which the mass transfer coefficient reached its peak. At this recycle rate, the exit VOC level was calculated to be 65 ppm.
No advantage to increasing the amount of recycle is realized once the mass transfer coefficient stops increasing. When the total flow through the module was increased to 0.08 mL/s, and 0.07 mL/s of the latex was recycled around the module, the exit VOC level was calculated to be 75 ppm, representing an increase of about 10 ppm. The optimum recycle rate is therefore 0.04 mL/s
| Number | Date | Country | |
|---|---|---|---|
| 61699921 | Sep 2012 | US |
