WASTE WATER TREATMENT

Abstract: A process for the reduction of organics in an adjusted brine solution is provided comprising contacting the ad­ justed brine solution with an aerated sludge of acclimated, aerobic bacteria under conditions sufficient to reduce the organics to a desired level. The waste water may be further treated by filtration, carbon adsorption and reverse osmosis or equivalent to treat the waste water for recycle or surface discharge.

Description: WASTE WATER TREATMENT This invention relates to the reduction of organic matter present in a brine solution. It is not uncommon to find organic material present in industrial waste waters, streams, ponds and other bodies of water containing brine. The organic matter, commonly called "organics", can be phenols, alcohols, ketones, esters, oligomes, polymer residues, proteins, carbohydrates, and fats. For example, in the production of poly (phenylene sulfide) organics such as easily dispersible low molecular weight poly(phenylene sulfide), poly(phenylene sulfide) by-products, and unreclaimed reactants such as p-dichlorobenzene and N-methyl-2-pyrrolidone (NMP) can accumulate. These organics and possibly others along with excess sodium sulfide and sodium chloride are present in the process brine waste water. The presence of these organics in brine solutions make it harder to dispose of them than if they were not present. In addition, regulations exist which stipulate the allowable level of Biochemical Oxygen Demand (BOD) and Chemical Oxygen Demand (COD) in surface water discharge. Therefore, processes which then will reduce the level of organic materials in a brine solution are highly desirable. Therefore, one object of the present invention is to provide a process for the reduction of the organic matter in a brine solution. Other aspects, objects and the several advantages of the present invention will become apparent from this specification and the claims, and the drawing which represent a schematic diagram of the invention. In accordance with the present invention, I have discovered that the level of organic matter present in an adjusted brine solution is reduced by contacting the adjusted brine solution with an aerated sludge of acclimated, aerobic bacteria under conditions sufficient to effect the reduction to a desired level. In the present invention, an adjusted brine solution is defined to be a solution whose pH and salt concentrations are adjusted to predetermined levels and thereafter maintained at these levels at as near a constant value as possible. This is because microorganisms grow best under constant environmental conditions. The addition of water is most commonly used to regulate the salt concentration value and the use of H2S04 is most common for the adjustment of p11 concentrations. Preferably, the pH should be adjusted to about 7.0 to 7.5 as microorganisms have been found to acclimate particularly well to this range. The brine solution will usually contain at least 2% wt. dissolved salts and more commonly from 2% to 10%. In the present invention, the salt concentration should be maintained at about 3.5 weight percent. The salts referred to in the process of this invention include salts of sodium, magnesium, calcium, barium, potassium, strontium, iron, nickel, and ammonia. The aerobic bacteria utilized in the process of the present invention are those present in general waste water or industrial water biotreatment process. The majority of these bacteria are gram negative. Representatives species of bacteria utilized in the process of the present invention include Escherichia, Proteus, Alcalegenis, Vibro, Aerobacter, Chromobacterium, Neissina, Pseudomonas, Spirillum, and Bacillus. Representative species of bacteria utilized in the process of the present invention include Escherichia coli, Proteus vulgaris, Alcalegenis faccalis, Vibro Netchnikovii, Aerobacter aerogenes, Chromobacterium prodigiosium, Neissina Catarrhalio, Pseudomonas fluorescens, Spirillum serpens and Bacillus brevis. The adjusted brine solution is contacted with an aerated sludge of aerobic bacteria under conditions sufficient to reduce the organics to a desired level. Generally the adjusted brine solution is contacted with an aerated sludge of bacteria wherein the oxygen concentration is from about .20 mg/liter to about 8 mg/liter. The temperature conditions for the contact will be in the range of from about 90F to about 1000F and the contact time will be in the range of from about .25 hrs. to about 10 days or until the desired amount of organic matter is reduced. Air is introduced into the microbial sludge contained in a tank by any conventional method known in the art, such as in the form of bubbles through diffusion or by turbulent agitation of the liquid by an impeller. The activated sludge process is maintained by returning a certain portion of the sludge that passes through the sludge tank and is settled out in a subsequent sedimentation basin. The aerobic bacteria are acclimated to the neutral pH and salt concentration conditions existing in the equalization pond before these bacteria are contacted with the brine solution. This is because time is needed for the bacteria to acclimate themselves to the eventual conditions to which they will be subjected. If the bacteria are contacted with a brine solution to whose p11 and salt concentration conditions they have not been previously adapted, then there exists the possibility that they will go into shock and therefore be unable to reduce the organic matter in the brine solution. As is known to one skilled in the art, the process of acclimating microorganisms to particular environmental conditions is a gradual process. At selected time intervals, the organisms are subjected to incremental additions of selected growth media until the total, desired concentration of growth media is achieved. During this process, some of the organisms will be non-viable while others will be able to sustain the growth conditions and multiply. The end result will be that by the time the total concentration by growth media is achieved, a population of viable microorganisms for this growth media will exist. The bacteria and other solids are normally removed by settling or coagulation and settling. If removals are insufficient further removals can be made by filtration. Filtration can be accomplished by any conventional process such as media bed filtration with or without coagulation; vacuum pressure filtration with or without filter aid, cartridge filtration and ultrafiltration. Additional organic matter may be removed by contacting the brine solution with activated charcoal as illustrated. In this manner, the Chemical Oxygen Demand (COD) is reduced. In addition, the brine solution may be desalted by well known desalination methods such as reverse osmosis and electrodialysis, optionally, after the brine has passed through an ultrafiltration-or other guard filters, Referring now to FIGURE I, polyphenylene sulfide process washwater containing concentrated brine and various organic substances is passed to an equalization pond where the pH and salt concentrations are subsequently adjusted to near constant levels. The adjusted brine solution is then contacted with an aerated sludge of aerobic bacteria under appropriate conditions to reduce the amount of organic matter present in the brine solution. The resulting treated brine solution is then contacted with a coagulant or flocculant, e.g., alum to aid in the setting of particles and is subsequently passed to a clarifier with part of the concentrated sludge passed as recycle to the biological treatment unit and part of it sent to drying beds, incineration, or other solids disposal methods. The supernatant brine is passed from the clarifier to media bed filtration. Subsequently the filtered brine solution is passed to carbon adsorption columns containing activated carbon wherein the amount of organic matter is further reduced. Effluent from the carbon adsorption columns then passes to ultrafiltration treatment for removal of very small dispersed particles and subsequently to a desalination unit wherein it is desalted by such typical processes as reverse osmosis, ion exchange or electrodialysis. The resulting treated solution should be essentially salt free and thus fresh water in nature. The following examples further illustrate the present invention: EXAMPLES Example I An experimental program was conducted to determine the effectiveness of activated sludge biological oxidation alone and following partial carbon adsorption on the treatment of polyphenylene sulfide plant process waste water for surface disposal. The plant process waste water contained over 3 wtx sodium chloride, which made it necessary to acclimate bacteria to both the dissolved organics and the high salt content of the waste water before evaluating the effectiveness of the biological treatment. Both the acclimation and biological treatment were carried out in the five-liter, Zaborstory, activated sludge unit shown in FIGURE 2. The apparatus is composed of a conical glass biodigester, a vertical glass-tube clarifier and auxilliary equipment. Air entering the digester from the bottom is dispersed by a built-in glass frit. The air provides oxygen for the bacteria and complete mixing. Waste water feed, nutrients, and recycle sludge enter the digester from the top. Digester pH was maintained in the 7 to 7.5 pH range by a pH controller. The digester temperature was maintained at about 750F. A more detailed description of the activated sludge unit shown in FIGURE 2 follows: A modified 8-liter cone-shaped glass perculator (Corning Glassworks, Corning, N.Y.; model number 7040-8L; upper diameter: 219 norm; length: 518 mm) was used as the biodigester (1). The waste water feed (3060 mg/liter Total Organic Carbon, 3.5 weight X NaCl) was charged through lines (3) and (3') by means of an Ultra Nasterflex peristaltic pump (5) (Cole-Palmer Instrument Company, Chicago, Illinois; model C-7555-20) having a pump head designed for a flow range of 0.378-378 ml/hr (Cole-Palmer; model C-7014-00,10). The feed was added at an average rate of about 380 grams per day. Nutrients (approximately 1 molar solutions of NH4Cl and K2HP04) were added through line (7) so as to provide a 100:5:1 weight ratio of chemical oxygen demand to nitrogen to phosphorus. Approximately 0.5 molar sulfuric acid was charged to the biodigester through line (9) by means of a small peristaltic pump (11) interfaced with a pH sensor (13) so as to maintain a pH of 7-8 in the biodigester. Enough air was introduced through line (15), rotometer (17) and a coarse glass frit (19) at the bottom of the biodigester to keep the aqueous system saturated with air. The bacterial floc was introduced through recycle line (21). The mixed liquor was allowed to flow from a mid-level exit tube (23) into a clarifier tube (25) of about 1 liter capacity, having an upper diameter of 2 inches and a length of about 30 inches. The clarifier (25) was fitted with a recycle line (32) which exited from the lower portion of the clarifier through a peristaltic pump at a rate of 10 to 30 ml per minute. The return line 33 to the clarifier exited about two inches below its withdrawal point of line 32.. Alum and caustic solutions were charged by means of small peristaltic Hasterflex pmps (27 and 29) to the recycle line 32. The flow of caustic to the recycle line was controlled by pH sensor 31 to 7.5 pH. The solution mixture was introduced into the clarifier (25) to form an aluminum hydroxide floc that aided in the settling of the bacteria floc from the biodigester. The alum content in the clarifier was maintained at dosages determined by jar tests (100-3000 mg/L). The clarifier content was stirred slowly (- 0.3 rpm) with stirrer (35) to mix biodigester effluent and alum flocculant solution. The settled bacteria floc was recycled to the biodigester (1) through line (21') by means of Ultra nasterflex pump (37) (Cole-Palmer; model C-7555-20) having a pump head designed for a flow range of 6.84-6840 ml/hr (Cole-Palmer; model C-7018-00,-10). The recycle flow rate was about 30-40 ml/minute. The effluent from the clarifier tube exited through line (39) and was collected in a large effluent bottle. Example II Gram-negative rod-shaped bacteria contained in an activated sludge of a municipal sewage treatment plant were acclimated to the highly saline waste water of a poly(phenylene sulfide) plant. The acclimation of the bacteria was carried at room temperature over a period of about 2 months in a laboratory treatment unit described in Example I. About 5 liters of an aqueous bacterial suspension having a mixed liquor suspended solids (MISS) content of about 3000 mg/liter (determined as Total Suspended Natter according to Procedure 209 D, "Standard Methods of Water and Waste Water", 15th Edition, 1980; APHA-AWWA-WPCF) and a mixed liquor volatile suspended solids (?fLVSS, "Standard Methods" procedure 209 E) content of about 60-88% of the NLSS content. Acetone was fed to the aqueous suspension at a rate of about 0.6 grams per liter per day so as to maintain a COD (Chemical Oxygen Demand, "Standard Methods' Procedure 508 A) loading of about 0.42 g COD/g #VSS/day, which was equivalent to about 0.5 g COD/g MLSS/day. Nitrogen and phosphorus nutrients were added in the form of aqueous solutions of NH4Cl and K BPO, so as to give a COD:N:P weight ratio of 100:5:1. The NaCl concentration of the aqueous system was gradually increased from 0 to about 35 grams per liter (3.5 weight % NaCl) by the incremental addition of 2 grams per liter three times a week. After an initial period of about 4 weeks, the aqueous bacteria suspension was fed, for 5 days, a mixture of 1.5 grams per liter per day (g/L-d) of acetone and 54 g/L#d grams per day of plant waste water containing about 3060 mg/liter TOC determined by means of an Oceanographic Carbon Analyzer (Oceanographic International Corporation, College Station, Texas). Thereafter, waste water without acetone was increased in two weeks from 100 to 375 g/L.d and continued at 375 g/L-d. Example III Seven aerobic biodigestion runs employing waste water having a pif of 9-9.5, 8 COD content of 5,000-10,000 mg/liter, a sulfide content of 100-500 mg/liter, and a salt content before adjustment of 3-6 weight percent were carried out, essentially in accordance with the procedure described in Example II. The salt content of the waste water was adjusted to about 3.5 weight percent by adding either NaCl or tap water. Table I Loading, Dissolved Feed Liquid Retention, Gram COD COD Removal, Run COD mg/L Days Gram MLVSS wt % Per Day 1 6300 3.8 0.7 75 2 6300 7.8 0.5 84 3 9400 7.2 0.6 86 4 9400 3.3 1.1 84 5 5800 4.8 0.7 87 6 5800 2.8 0.9 89 7 5720 2.7 1.0 91 Data in Table I show that 75-86X of COD can be removed from process waste water by biological treatment in accordance with the process of this invention. Slightly higher COD removal (87-91%) was achieved by prior treatment with activated carbon with the dosage set to remove about 30% of the COD. Example IV In this example the feasibility of removing residual TOC (Total Organic Carbon) from biologically treated waste water is demonstrated. Several samples of-biologically treated waste water containing about 750 mg/L COD were mixed with two different types of activated carbon: Nuchar 2 WVG, a bituminous charcoal having a surface area of about (900 m marketed by the Carbon Department of Westvaco Corporation, Covingtan, Virginia, and Hydrodarco 3000, a lignite-derived charcoal having a 2 surface area of about 600 n2/g marketed by ICI Americas, Inc., Wilmington, Delaware. Bottles containing biologically treated waste water and activated charcoal were agitated for about 15 hours by means of a platform shaker operated at a frequency of 2-3 oscillations per second. Results summarized in Table II show that about 76-87% of residual TOC can be recovered by treatment with 1-5 weight percent of activated carbon. Table II Type of Dosage of Activated TOC Removal From Activated Carbon Carbon (Weight-%) Waste water (Weight- > Nuchar WVG 0.1 31.5 Nuchar WVG 0.3 58.5 Nuchar WVG 1.0 81.1 Nuchar WVG 5.0 87.3 Hydrodarco 3000 0.1 19.6 Hydrodarco 3000 0.3 33.6 Hydrodarco 3000 1.0 75.5 Hydrodarco 3000 5.0 82.9 Reasonable variations and modifications are possible from the foregoing without departing from the spirit of this invention.

Claims: Claims 1. A process for reducing the level of organic matter present in an adjusted brine solution, c h a r a c t e r i z e d b y contacting said adjusted brine solution with an.aerated sludge of acclimated aerobic bacteria. 2. The process of claim 1 characterized in that said aerated sludge of acclimated aerobic bacteria has an oxygen concentration from 0.20 to 8.0 mg 02/liter. 3. The process of claim 1 or 2 characterized in that said contacting is carried out at a temperature from -13 to +38 C. 4. The process of any of claims 1 - 3 characterized in that said contacting is carried out for a period of time from 0.25 hrs. to 10 days. 5. The process of any of claims 1 - 4 characterized in that the salt concentration of said adjusted brine solution is Sn the range from 2 to 10 weight percent. 6. The process of any of claims 1 - 5 characterized in that the pH of said adjusted brine solution is in the range from 7.0 to 7.5. 7. The process of any of claims 1 - 6 characterized in that the resulting reduced brine solution is filtered; in particular wherein the resulting filtered brine solution is contacted with activated charcoal. 8. The process of any of claims 1 - 7 characterized in that the salt concentration of the brine solution is reduced by reverse osmosis. 9. The process of any of claims 1 - 8 characterized in that said bacteria are selected from at least one genus of Escherichia, Proteus, Alcalegenis, Vibro, Aerobacter, Chromobacterium, Neissina, Pseudomonas, Spirillum and Bacillus. 10. The process of claim 9 characterized in that said bacteria are selected from at least one species of Escherichia coli, Proteus vulgaris, Alcalegenis faccalis, Vibro Metchnikovii, Aerobacter aerogenes, Chromobacterium prodigiosium, Neissina Catarrhalio, Pseudomonas fluorescens, Spirillum serpens and Bacillus brevis.

Inventors: BUCHANAN, BEN BREVARD
Applicants: PHILLIPS PETROLEUM COMPANY
Application year: 1983
Main classification: C02F3
IPC codes: C02F9, C02F3, C02F1