METHOD OF IMMOBILIZING ORGANIC CONTAMINANTS AND NON-FLOWABLE MATRIX PRODUCED THEREFROM

Abstract: A method for treating polar or aqueous fluid compositions containing an amount of an organic contaminant to immobilize the contaminant by forming a non-flowable matrix containng the contaminant. The non-flowable matrix can be easily disposed of. The method comprises adding a sufficient amount of organoclay to the fluid composition to absorb substantially all of the organic contaminant. A sufficient amount of solid adsorbent is added to the composition to absorb or react with substantially all of the polar fluid or water to form a substantially non-flowable matrix. Typically, such polar fluids or aqueous compositions are in emulsion form with the organic contaminant, and the addition of the organoclay breaks the emulsion, permitting removal of a portion of the water or polar fluid from the composition to thereby reduce the volume to be disposed of. The method of this invention immobilizes the organic contaminant, in such a manner that it is non-leachable from the matrix.

Description: Description Method of Immobilizing Organic Contaminants and Non-Flowable Matrix Produced Therefrom This application is a continuation-in-part of my copending application Serial No. 307,300, filed on September 30, 1981, and entitled "Organoclay Waste Disposal Method." The entire disclosure of this parent application is incorporated herein by reference. Background of Invention Technical Field: This invention relates to a method for treating waste fluids containing organic contaminants to solidify the waste fluid to facilitate disposal; and more partic¬ ularly relates to the forming of a* substantially non- flowable matrix from an aqueous waste fluid containing organic contaminants. Background Art: One of the major problems facing cities, chemical manufacturers, and industries using various chemicals is waste disposal. This problem can generally be divi¬ ded into three major categories: solidification of fluid waste, disposal of waste by land burial, and re¬ medial action around existing disposal sites which are now leaking. The use of finely divided or porous solid mater¬ ials to solidify fluid wastes and spills is well known. Generally, the purpose of solidification is to aid in the disposal of fluid wastes or spills. Among the materials which have been used for solidification are cement, kiln dust, fly ash, 'soil, and sawdust. These materials have numerous disadvantages. The volume of solidified waste is usually four to five times the vol¬ ume of the original waste. Additionally, these dusts and the like generally have no specific affinity for one component of the waste relative to another and, even after solidification, liquid components may leach from the waste. Liquid wastes containing five percent (5%) or more of organic contaminants also disrupt the cementatious reactions that help stabilize cement and kiln dust waste products. These current techniques of waste solidification generally physically trap the organic waste in a solid matrix. When the solid matrix is breached, the organic waste is released unabated to the ground water. Another problem that plagues this method of waste disposal is that during the solidification process, the liquid phase and the solidification medium have a tendency to separate. This renders the method ineffective at sta- bilizing the waste. One method that has been reported for overcoming this problem is to mix small portions of bentonite with portland cement; this eliminates the aqueous phase separation problem. The bentonite, how¬ ever, does not adsorb the organic waste. This technol- ogy still suffers from the inadequacy of not binding the organic waste other than by physically trapping it. Prior art of which applicant is aware which relates to solidification of fluid waste are as follows: __***ϊ t y-! —*-**- ? *_-* B a-* * " ** - '"'— f—r 'rw'w.ji , ,^ 1 . 1 w . - ^_t __.__. i -BUREAU OMPI British Patent No. 1,280,373 to Davies et al describes the separation of an oil from an emulsion. Several methods are enumerated for forming the emulsion into two layers for evaporation of the aqueous layer. One of these methods utilizes a mixture of surface- active clay and a polyelectrolyte. First the surface- active clay and then a polyelectrolyte is added to the emulsion. Bentonite is described as a particularly suitable clay. Polyamides are described as particularly suitable polyelectrolytes. U.S. Patent Number ' 3,274,784 to Shock et al, de¬ scribes a method for the disposal of radioactive waste. This is accomplished by forming a solidifiable composi¬ tion containing the radioactive waste in the form of a solution or slurry in water and mixing with clay miner¬ als, lime and caustic present in proportions to provide a solid mass on standing. The radioactive wastes con¬ tain fissionable products such as strontium, cesium, ruthenium, etc. The preferred clay is calcium montmor- illonite. Bentonite was found to require temperatures too high for solidification to take place. Natural clays may also be used. ' U.S. Patent No. 3,948,770 to Goodrich et al de¬ scribes the use of an anionic polyelectrolyte and a sodium or a calcium montmorillonite clay to effectively separate water oil droplets in sea water. U.S. Patent No. 4,033,764 to Colegate et al de¬ scribes scavenging metal ions from solution by means of a complexing agent comprised of an inorganic substrate, such as a clay mineral, with covalent organic molecules, such as onium compounds, chemically bonded to the sub¬ strate. U.S. Patent No. 4,149,968 to Kupiec, describes the use of bentonite clays and portland cement in aqueous -" " aa —» <_.£ OΛΪPI solutions containing polluting materials, e.g. metallic ions, to form a solid mass. Japanese - 015979 to Koyo Kasei KK, describes the detoxification of PCB-containing waste water by mixing the waste water with diatomaceous earth, bentonite or other clay which has been made lipophilic, and then mixing with cement, water, and aggregate. In the method, less than 20% PCB waste liquor, sludges, etc., are mixed with the diatomaceous earth, bentonite, or clay minerals of inorganic fine particles previously made lipophilic by surface treatment. The PCB's are allowed to be adsorbed on the mineral, and then the resulting materials are mixed with cement, water, and aggregate. Diffusing or leaching appears to be reduced. Activated carbon or silica gel may also be used in place of the clay. Organoclays are well-known in the art, see for example the following U.S. patents: 2,531,427 to Hauser; 2,966,506 to Jordan; 3,422,185 to Kuritzkef; 3,974,125 to Oswald; 4,081,496 to Finlayson; and 4,105,578 to Finlayson et al None of these aforementioned references teach or suggest the use of these organoclays to immobilize or¬ ganic contaminants to facilitate their disposal. Summary and Objects of the Invention A method is provided for treating polar or aqueous fluid compositions containing an amount of an organic contaminant to immobilize the contaminant by forming a nonflowable matrix containing the contaminant. The non- SϋGSTITUΪE SHEET OMPI flowable matrix can be easily disposed of. The method comprises adding a sufficient amount of an organoclay to the fluid composition to absorb substantially all of the organic contaminant. A sufficient amount of solid adsorbent is added to the composition to absorb or react with substantially all of the polar fluid or water to form a substantially non-flowable matrix. Typically, such polar or aqueous compositions are in emulsion form with the organic contaminant and the addition of the organoclay breaks the emulsion, permitting removal of a portion of the water or polar fluid from the composition to thereby reduce the volume to be disposed of. The method of this invention immobilizes the organic contam¬ inant, in such a manner that it is non-leachable from the matrix.. It is thus an object of this invention to provide a method for treating fluid wastes, e.g. ponds, streams, etc., to immobilize the organic contaminants contained therein to faciliate disposal. It is a further object of this invention to provide a method for treating both aqueous and polar fluid waste containing such organic contaminants to facilitate dis¬ posal. It is a further object of this invention to provide a method for immobilizing organic contaminants contained in a fluid waste, so that they do not leach out into the environment, which method substantially reduces the volume of the waste to facilitate disposal. It is a further object of this invention to provide a method for treating fluid waste containing organic contaminants emulsified therein, to "break" the emulsion to permit removal of of water to reduce the volume and to immobilize the organic contaminants. It is a yet further object of this invention to ^J i_Sm_ i k w I --__ - i -__-_-. I immobilize organic contaminants contained in a fluid waste so that the volatility of the organic contaminant is substantially reduced. It is a still further object of this invention, to provide a method for treating fluid waste containing organic contaminants, to substantially reduce the volume of the waste so that it may be more economically trans¬ ported to a wste site and disposed of. It is yet a further object of this invention, to provide a method for treating fluid waste to form a sub¬ stantially nonflowable matrix. It is a further object of this invention, to pro¬ vide a method for treating fluid waste to immobilize the organic contaminants contained therein, using materials which have a specific affinity for the organic contamin¬ ant, and consequently, preferentially absorb the contam¬ inants to prevent leaching and volatilization. It is a yet further object of this invention, to provide a substantially non-flowable matrix containing organic contaminants which can be easily disposed of. Brief Description of the Figures Figure 1 is a graph showing the relationship of the logarithm of the distribution co-efficient of certain organic contaminants with the logarithm of their solu- bilities in water. Figure 2 is a graph illustrating organic emissions from a simulated land farm disposal of petroleum sludge. Figure 3 is a graphical representation of the se¬ quential leaching of a solidified waste containing 1% hexachlorocyclopentadiene and 1% ethyl parathion (Exam¬ ple 9). Figure 4 is a gas chromatagraphic (GO analysis of SUBSTITUTE SHEET y OMPI - 1 - the leached original waste and the leached solidified product of this invention (Example 10). Disclosure of The Invention Organoclays are well known in the art as exempli- fied by the aforementioned patents to Hauser, Jordan, Kuritzkey, Oswald et al, Finlayson, and Finlayson et al, the entire disclosures of which are incorporated herein by reference. In this invention, the term "organoclay" refers to various clay types, e.g. smectites, that have organo ammonium ions substituted for cations between the clay layers. The term "organo ammonium ion substi¬ tuted" refers to a substituted ammonium ion in which one or more hydrogen atoms are replaced by an organic group. The organoclays are essentially solid compounds that have an inorganic and organic phase. The preferred clay substrates for use in this in¬ vention are the smectite-type clays, particularly the smectite-type clays which have a cation exchange capa¬ city of at least 75 millequivalents per 100 grams of clay. Useful clays for such purposes include the natur¬ ally occuring Wyoming variety of swelling bentonite and similar clays, and hectorite, which is a swelling magne- siumlithium silicate clay. The clays, are preferably converted to the sodium form if they are not already in this form. This can be effected, by a cation exchange reaction with a soluble sodium compound. These methods are well-known in the art. Smectite-type clays prepared synthetically can also be utilized, such as montomoril- lonite, bentonite, beidelite, hectorite, saponite, and stevensite. The organoclays useful in this invention include those set forth in U.S. Patent No. 2,531,427 to Hauser. These organoclays are modified clays which exhibit in organic liquids, some of those characteristics which un¬ treated clays exhibit in water. For example, they will swell in many organic liquids and will form stable gells and colloidal dispersions. Generally, the quaternary ammonium salt substituted onto the clay has organic groups attached to the clay which will range from aliphatic hydrocarbon of from 1 to 24 carbons to aromatic organic molecules, such as benzyl groups that could have a host of groups substituted on the benzyl ring. The number of benzyl versus straight chain hydrocarbons substituted on the ammonium ion can vary from 3 to 0 (i.e. dimethyl dioctododecyl 0:2, methyl benzyl dioctododecyl 1:2, dibenzyl dioctobenzyl 1:1, tribenzyl octadecyl 3:1, methyl dibenzyl octodecyl 2:1). The amount of alkyl ammonium salt substituted on the clay can vary between 0.5%- to 50%. In particular, the preferred organoclay used in this invention comprises one or more of the following quaternary ammonium cation modified montmorillonite clays: R2 I + I i Rj— —R4 I Montmorillonite I I . *3 L wherein R * j_ is an alkyl group having at least 10 carbon atoms and up to, for example, 24 carbon atoms, and pref- erably having a chain length of from 12 to 18 carbon atoms; 2 is hydrogen, benzyl or an alkyl group of at least 10 carbon atoms and up to, for example, 24 carbon atoms, and preferably from 12 to 18 carbon atoms; and R3 SUC5757U7Ξ SHEET and R4 are each hydrogen or lower alkyl groups, viz. , they contain carbon chains of from 1 to 4 atoms, and preferably are methyl groups. Other organoclays utilizable in the invention in¬ clude benzyl organoclays such as dimethyl benzyl (hydro- genated tallow) ammonium bentonite; methyl benzyl di(hy- drogenated tallow) ammonium bentonite; and more general¬ ly quaternary ammonium cation modified montmorillonite clays represented by the formula: Rl R 2 — —R4 Montmorillonite R3 wherein R * j_ is CH3 or C5H5CH2; R2 is C 6 H 5 H 2' and R 5 and R4 are alkyl groups containing long chain alkyl radicals having 14 to 22 carbon atoms, and most prefer¬ ably wherein 20 to 35% of said long chain alkyl radicals contain 16 carbon atoms and 60% to 75% of said long chain alkyl radicals contain 18 carbon atoms. The montmorillonite clays which may be so modified are the principal constituents of bentonite rock, and have the chemical compositions and characteristics de¬ scribed, for example, in Berry and Mason, "Mineralogy", 1959, pp. 508-509. Modified montmorillonite clays of this type in (i.e. organoclays) are commercially availa¬ ble from Southern Clay Products, Inc., Gonzales, Texas under such trade designations as CLAYTONE 34 and 40, and are available from NL Industries, Inc., New York, New York under such trade designations as BENTONE 27, 34/ and 38. The preferred organoclays utilized in this in- vention, are the higher dialkyl dimethyl ammonium organ¬ oclays such as dimethyl di(hydrogenated tallow) ammonium bentonite; the benzyl ammonium organoclays, such as dimethyl benzyl (hydrogenated tallow) ammonium benton- ite; and ethylhydroxy ' ammonium organoclays such as methylbis (2-hydroxyethyl) octodecyl ammonium bentonite. The fluid waste, which may be an aqueous waste or a waste fluid whose carrier fluid is a polar composition, e.g. aliphatic alcohol, etc. contains an amount of or- ganic contaminant. Typical organic contaminants are the chlorinated organic compounds, e.g. DDT, BDD, DDE, 2, 4-dichloro-phenol, tetrachloroethylene, and other organics such as benzene, toluene, meth lene chloride, chloroform, 1, 2 dichloroethane 1, 1, 1- trichloroeth- ane, trichloroethylene, tetrachl ro ethylene, 2-nitr- ophenol, pentachlorophenol, dimethy phthalate, Lindane, Arochlor-1254, ethyl benzene, HCP, parathion, dichloro- benzene, hexachlorocyclopentadiene, eth lparathion, 2, 4-dinitrotoluene, naphtalene, pyrene, etc. In the method of this invention, a sufficient amount of the organoclay is added to the aqueous or polar fluid composition to adsorb substantially all of the organic contaminants on the organoclay. Preferably, the amount of organoclay is at least about one percent (1%) by weight of the amount of organic contaminant and most preferably at least about five percent (5%) by weight of the organic contaminant. If too little organo¬ clay is used, there will be insufficient solidification. The upper limit of organoclay is primarily dictated by - cost. For general guidance, however, about ten percent (10%) by weight of the amount of the organic contaminant is a preferred upper limit. The organoclay is mixed thoroughly with the fluid waste. The temperature at which the organoclay is mixed €? '-' ϊ — ••■ • • — - ■**" _ *•■*• : -7= » τ - -• t -, » r a «f. a & _^r_ Q P A ? *■ ■tϋ ώ i l i . ι__ S_ _.__ 1 /- ^ BU KtΛ i .. O PI with the waste is not critical, with room temperature being preferred for obvious cost considerations. The organoclay, upon mixing in the fluid waste, swells as the organic contaminant molecules are sorbed into and onto the organoclay. All current solidific¬ ation technology only physically traps the organic contaminant molecules in voids in a solid matrix. The use of the organoclay helps to overcome this problem and tends to prevent separation of the organic contamin- ants during the solidification process. The organoclay additionally fixes the organic contaminant compounds through absorption involving partitioning of the organic molecules of the contaminant into the organoclay. This invention retains the advantages of retarding phase separation exhibited by the use of untreated bentonite and adds the extra advantage of fixing the organic con¬ taminant in a physical chemical way rather than merely occluding it. This results in a solid phase that is far less leachable than with other known techniques. The organic molecules of the contaminant preferably partition into the organic phase of the organoclay versus the aqueous phase or polar fluid phase. The magnitude of organic partitioning of a given organic molecule into the organoclay over, for example, the aqueous phase, can be predicted qualitatively by the solubility of the organic molecule in the aqueous phase. That ' is to say, an organic molecule that is very insolu¬ ble in an aqueous phase will partition very strongly into the organoclay relative to a more soluble organic molecule. This partitioning phenomenom also follows chromatagraphic theory which allows precise predictions of how organic molecules will migrate through a bed of organoclay. Figure 1 shows the linear relationship ' of distribution co-efficients for several key organic spe- wς,w , , , υ i a «S «E B -BU REAU O PI cies with three forms of organoclay. The distribution coefficients equals the amount of organic adsorbed in the clay divided by the amount left in solution times the volume of the solution divided by the mass of the clay. The aqueous solution contains the organics listed in Figure 1. Generally, the amount in solution depends on solubility. Broadly, the next step in the method of treating the waste fluid or liquor is adding a sufficient amount of solid adsorbent to adsorb or react with substantially all of the water therin to form a substantially non- flowable matrix. Solid adsorbants that may be utilized in this invention are portland cement, kiln dust, fly ash, clay, soil or attapulgite or mixtures thereof, e.g. attapulgite and cement. The appropriate ratio of solid adsorbent to be added to the organoclay waste mixture can vary from about zero (0) (when the organoclay alone is sufficient to solidify the waste stream) up to fifty percent (50%) by weight of the organic contaminant, al- though up to about one-hundred percent (100%) by weight of the organic contaminant may be added. The preferred lower range is about ten percent (10%) solid adsorbent. The addition of the solid adsorbant solidifys the mix¬ ture into a substantially non-flowable matrix containing an amount of water and an amount of organic contaminant molecules partitioned and bound within the organic phase of the organoclay portion of the solid matrix. In a preferred embodiment of this invention, after the step of adding the organoclay, a portion of the water or polar fluid is removed, for example, by decant¬ ing or otherwise separating the fluid from the composi¬ tion. Such procedure substantially reduces the volume of the solidified matrix. The organoclay when added to the fluid waste composition tends to break organic OiϊiPI < IPO contaminant water emulsions. The organoclays are very effective at breaking emulsions at extremely low dose rates of organoclay. The breaking of the emulsion is particularly useful if the waste is to be solidified, 5 for less mass must be solidified when water is removed,- and this therefore provides for decreased cost in transportation and disposal. The water can also be recovered for further use. Additionally, this water removal or decanting step provides for the waste being 10 incinerated at considerable savings since the BTU value of the waste has increased substantially by the exclu¬ sion of water. Still further, the organics left in the waste mass can be recovered for reuse and the organo¬ clay regenerated. 15 Another aspect of this invention is providing a substantially non-flowable matrix comprising an amount of water or polar fluid, an amount of organic contamin¬ ant in the water or polar fluid, a sufficient amount of organoclay to absorb substantially all of the contamin- 20 ants, and a sufficient amount of solid adsorbant to adsorb or react with substantailly all of the water or polar fluid to thereby form the substantially non-flow¬ able matrix. The method of this invention provides for several 25. advantages which include substantially reducing the volume and mass of a finally solidified product compared to known prior art methods of solidifying waste. This yields substantial savings in mixing, transportation and disposal site costs. Additionally, the organic 30 contaminant/water emulsions can be broken by the use of the organoclays, thus yielding further volume reduction and allowing water to be returned to the plant for fur¬ ther use. Removal of water also makes incineration more feasible since the solid matrix has a high BTU SHEET value. Still further, volatile emissions originating from the waste mass are substantially reduced by the method of this invention. This is important for the health and safety of workers and of residents who live near the disposal site. And finally, the leach rates of the waste are substantially reduced, thus lowering the environmental liability associated with disposal. Example 1 In order to demonstrate the efficacy of the organo- clay used in this invention, several batch sorption ex¬ periments were performed with two forms of higher dial- kyl dimethyl organoclay and compared to untreated mont¬ morillonite sorption. These were conducted with 100:1 solution to solid ratio. The following Tables 1, 2 and 3 are a summary of these studies showing results from batch equilibration sorption studies of a montmorillon¬ ite, which has not been rendered into an organoclay, CLAYTONE ® 34, and CLAYTONE ® 40 respectively. CLAYTONE ® 34 and CLAYTONE ® 40 are organoclays, each being a dimethyl di(hydrogenated tallow) ammonium bentonite product, available from Southern Clay Products, inc. of Gonzales, Texas. It can be seen that extremely efficient removal occurs for all of the listed organics with the organo- clays. The analyses for the majority of compounds in Tables 1, 2 and 3 were conducted by standard gas chro - atographic techniques. , The data for benzene, toluene and methylene chloride in these Tables are less accurate because the measurements were conducted by determining only the total organic carbon concentration. <__? ___.- ^ ΪTU7E SHEET O PI Table 1 24 Hours Batch Equili¬ 48 Hours Batch Equili¬ bration Concentration bration Concentration Inlet Con- Concen- centrations tration Amount Blank Amount Blank Organic Spiking Level in Blank Recovered (ppb) % Recovered (ppb) % Species (ppb)(jαg/l) (ppb)(ug/l) (ppb)(ug/) (ug/1) Sorbed (ppb)(μg/l) (μg/1) Sorbed π Aroclor 1254 3.65 0 4.95 0 0 13 0 0 p,p*-DDT 0.88 0 0.82 0 7 ' 0.96 0 0 o,p'-DDT 1.77 0 2.11 0 0 2.16 0 0 C p,p'DDD 0.75 0 0175 0 0 0.88 0 0 o,p'DDD 0.43 0 0.46 0 0 0.36 0 16 H ω Ui p,p'-DDE 0.56 0 0.68 0 0 0.86 0 0 m o,p'-DDE 0.17 0 0.20 0 0 0.15 0 12 ■ 4 2,4-Dichloro- phenol 18,000 11,000 39 11,000 39 Tetrachloro- ethylene 318 0.20 278 2.10 13 331 0.7 Benzene 1.35 x 10 5 0 1.35 x 10 0 0 Toluene 5.4 x 10 4 0 4.54 x 10 8 16 Table 2 24 Hours Batch Equili¬ 48 Hours Batch Equili¬ bration Concentration bration Concentration Inlet Con- Concen- centrations tration Amount Blank Amount Blank Organic Spiking Level in Blank Recovered (ppb) % Recovered (ppb) % Species (ppb)(ug/l) (ppb)(jug/l) (ppb)(ug/) (ug/ ) Sorbed (ppb)(ug/l) (ug/1) Sorbed ( Aroclor 1254 3.65 0 0 0 100 0 0 100 F'3 p,p'-DDT 0.88 0 0 0 100 0 0 100 o o,p'-DDT 1.77 0 0 0 100 0 0 100 ,p » DDD 0.75 0 0 0 100 0 0 100 c o,p'DDD 0.43 0 0 0 100 0 0 100 H a-. p,p » -DDE 0.56 0 0 0 100 0 0 100 (!) o,p'-DDE 0.17 0 0 0 100 0 0 100 2,4-Dichloro- phenol 1 188,,000000 200 99 200 99 Tetrachloro- ethylene 3 31188 0.20 25 0.3 92 24 0.2 92 Benzene 1133..55 xx 1100-55 0 5400 0 96 Toluene 55..44 xx 1100 44 0 2160 0 96 Methylene Chloride 5.12 x 10 5 1.08 x 10 5 79 Table 3 24 Hours Batch Equili¬ 48 Hours Batch Equili¬ bration Concentration bration Concentration Inlet Cori- Concen- centrations tration Amount Blank Amount Blank Organic Spiking Level in Blank Recovered (ppb) % Recovered (ppb) % Species (ppb)(ug/l) (ppb) (jug/) (ppb)(ιg/) (ιιg/1) Sorbed (ppb)(ug/l) (ug/1) Sorbed Aroclor 1254 3.65 0 0 0 100 0 0 100 11) c p,p'-DDT 0.88 0 0 0 100 0 0 100 03 o,p'-DDT 1.77 0 0 0 100 0 0 100 p,p'DDD 0.75 0 0 0 100 0 0 100 c o,p'DDD 0.43 0 0 0 100 0 0 100 H r ~ ι p,p'-DDE 0.56 0 0 0 100 0 0 100 CD 0,p'-DDE 0.17 0 0 0 100 0 0 100 2 ,4-Dichloro- m phenol 18,000 200 99 200 99 H Tetrachloro- ethylene 318 0.20 27 0.3 92 25 0.30 92 Benzene 1.35 x 105 0 3420 0 76 Example 2 The following Table 4 provides an initial compar¬ ison of literature values of sorption capacities of activated charcoal for several organic compounds and sorption capacities from experimental data for the di¬ methyl ditallow form of the organoclay for these or¬ ganic compounds. The data for charcoal was taken from EPA Report 600/8-80-23 and for the organoclay from data based on a single experimental value per compound. Table 4 Sorption Capacities (mg/g) Organic Compound Charcoal Organo-Clay Benzene 0.1 18 Toluene 25.0 6 Methylene Chloride 1.2 49 Example 3 The superiority of the organoclay for sorption of organics was further investigated. The sorption of three forms of organoclay at various loading rates for 12 priority organics in water were compared with activa¬ ted charcoal in laboratory experiments and these results are shown in the following Table 5. -BU EA O OMMPPII λ- WIPO Table 5 Percentages of Sorpt ion Concen¬ Dimethyl Benzyl | Di( ydrogenated |Methylbis (2-hydrox- | tration (Hydrogenated Tallow) | Tallow) lyethyl) Octodecyl | Car¬ of Organ- Clay Type j Ammonium Bentonite | Dimethyl Ammonium |Ammonium Bentonite | bon c ic ug/1 Bentonite 1 (ppb) Clay Dose(mg/L) | 130 660 1300 | 130 660 1300| 130 660 1300 | 130 (;) 1 1,000 Chloroform 64 49 56 47 55 43 | 42 49 51 27 1,000 1,2 Dichloroetha 46 36 50 48 49 42| 34 29 36 40 1,000 1,1,1 Trichlore- 1 thane 60 55 54 40 49 40 | 36 43 45 30 -r in •43 ϊn 1,000 Trichloroethylen 27 24 25 12 43 9| 5 13 22 86 1,000 Tetrachlorethylen€ i 85 46 74 47 51 74| 11 39 60 I 92 700 2 Nitrophenols 84 87 99 96 ND 27 92 87 97 94 49 84 91 95 97 96 85 750 Pen achlorophenol ND ND ND | ND ND ND| ND 94 92 ND • | 94 400 Dimethyphthala e 85 ND ND | 92 94 ND ND| 70 ND ND | 92 400 Lindane | 99.7 93 ND ND | 99.9 85 ND 98 ND| 99.9 ND ND | 100 Arochlor 1254 | 40 29 90 88 95 94 | 88 77 98 90 98 95 81 74 84 65 92 89 | 99.7 Example 4 Experiments were conducted on solidifying indus¬ trial Class I toxic wastes. The organoclay utilized was a dimethyl di(hydrogenated tallow) ammonium benton- ite. It was found that about ten percent (10%) organo¬ clay by weight of the solidified matrix is sufficient to solidify the waste. The solidified waste had dras¬ tically reduced volatile organics emanating from it. This is reflected in organic sniffer results in Table 6. These solids can be handled easily with convention¬ al equipment such as trucks and front-end loaders. It was also determined that leaching of the solidified waste reduces the amount of organics that leach into the aqueous phase from 200 ppm to 20 ppm. • F-. : : ** * Γ ..T__ acr-Γ-?iiL.-εH--Γc * Table 6 . Sniffer, ppm in Gas Phase 20% waste, 2% organoclay 18 78% kiln dust 20% waste, 5% organoclay 75% kiln dust 20% waste, 10% organoclay 70% kiln dust 20% waste, 80% kiln dust 90 20% waste, 2% organoclay 78% fly ash 20% waste, 5% organoclay 75% fly ash 20% waste, 10% organoclay 70% fly ash 20% waste, 80% fly ash 90 SUBSTk \ 5ϋ -' i SHEET Example 5 Volatile organics emanating from landfarm disposal of petroleum sludge can be reduced by ^application of organoclay. Figure 2, A and B, illustrate, respective- ly initial emissions from an untreated landfarm waste in soil and landfarm waste which was treated in soil with a thin layer of organoclay sprinkled onto the waste bur¬ dened surface. The magnitude of the emissions resulted from physically disturbing the landfarmed waste by disk- ing or tilling, a normal commercial practice. Figure 2, C and D, illustrate, respectively, the volatile organic concentration resulting from tilling the organoclay treated surface 24 and 72 hours after treatment. It can be seen that after the first disking, the emissions were reduced essentially to background levels. For up to ten days after the initial waste implacement, this same low level quantity of emissions occured even when the landfarm was disked repeatedly. Applications of organo¬ clay also tended to solidify the waste-burdened surface producing a mechanically superior surface, vehicles could travel over the organoclay treated area sooner af¬ ter the waste was applied. Currently, industrial land¬ farm operations are delayed about three days between waste applications to ensure that there is a stable sur- face for heavy equipment. It is not uncommon for land¬ farm vehicles to become stuck in areas where the wastes are not percolating into the soil rapidly enough to ac¬ commodate a mechanically stable surface. Application of organoclay to these surfaces alleviated this situation. S UBCTITUTE SHEET Example 6 The solidification of organic waste with organo¬ clays also has the advantage of reducing the final dis¬ posal volume of the solidified waste. Table 8 contains examples of two wastes solidified in a conventional way versus solidification with the method of this invention using an organoclay. Table 7 Volume of Volume of Conventional Organoclay Solidification (yd**--) Solidification (yd 3 ) 1 square yard of class 1 toxic waste 4 1.4 1 square yard of class 2 toxic waste 4.97 1.1 Example 7 In one series of tests a specific waste containing about forty percent (40%) water by weight was solidified according to established practice and by the method of this invention, with and without decanting. The organo¬ clay utilized was a dimethyl di(hydrogenated tallow) ammonium bentonite. Details are set out in Table 8. It can be seen from Table. 8 that the major advanta¬ ges of this invention are achieved. SUBSTITUTE SHEET Table 8 Solidification of an API (American Petroleum Institute) Separator Sludge with Conventional Fly Ash Treatment and the Method of This Invention Method of the Invention Conven- Without With tional 4 Decanting Decanting, Volume of Waste (cc) 1,000 1,000 1,000 Weight of Waste (g) 890 890 890 Weight of Fly Ash (g) 3,846 Weight of Organo-Clay (g) — 22 22 Weight of Attapulgite (g) — 423 180 Weight After Solidification (g) 4,736 1,335 1,092 Volume After Solidification(cc) 4,850 1,550 800 Sniffer Test (ppm in gas phase)*-- 90 ■ <1 <1 TOC 3 in Leachate (ppm) 2 50 20 1 Samples were placed in capped bottles and allowed to stand for 24 hours. The head space in the bottles was then measured with a TLV sniffer that was standardized against methane. 2 The waste was leached in a pH-adjusted neutral water solution for 24 hours with a ratio of 10:1 for water to waste. 3 TOC - Total Organic Content. 4 Fly ash only. suc rrrurΞ SHEET Example 8 The waste of Example 7 was approximately forty per¬ cent (40%) water. A waste with low percentage water and high viscosity was solidified. The results are shown in Table 9. In this case, the volume also was substantially reduced. This can result in substantial savings in mix- xing, transportation, and disposal site cost. Table 9 SOLIDIFICATION OF A VISCOUS WASTE THAT CONTAINS LESS THAN 10% WATER Method of Conventional Inventionl Volume (cc) 1,000 1 , 000 Weight of Waste (g) 930 930 Weight of Fly Ash (g) 2,150 Weight of Organoclay (g) — 23 Weight of Attapulgite (g) 288 Weight After Solidification (g) 3,080 1. , 241 Volume After Solidification (cc) 3,300 1 , , 300 - ■• No decanting. The clay utilized was a dimethyl di(hydrogenated tallow) ammonium bentonite. r*? Tr~-i-~~r- * - ***** T ;τ_ <_, ϊiε. ET Example 9 In order to illustrate more quantitatively the change in leach rate achievable by employing the inven¬ tion, a third waste containing 8% dichlorobenzene, 1% hexachlorocyclopentadiene, and 1% ethyl parathion was solidified and leached. The solidifications were con¬ ducted employing .5, 1, 2, 4, 8, and 15 grams of the organoclay and 5 milliliters of waste. The leachings were conducted for 24 hours. The results for the first batch leaching results are given in Table 10. It can be seen that substantial lowering of leach rate was ob¬ tained. A second batch leaching was performed on the same waste and the results of that leaching can be seen in Table 11. The leach rate was reduced even further in this second sequential leach. The results of these two leachings are presented graphically in Figure 3. c*ι i -d. ' s ' i Ϊ ϋ E SHEET / ^BU EAt OMPI 4 . wire Table 10 Leaching Results for Solidified Waste Containing 1% Hexachloropentadiene and 1% Ethyl Parathion pH 3 pH 7 pH 11 .5 0% 12.9% 3.4% 38.1% 4, .9% 81.4% *100% is defined as the amount that leaches from conventional solidification Table 11 Percent of Organics Leached in Second Batch Equilibration for Waste Containing 1% Hexachloro- pentadiene, 1% Ethyl Parathion, and 8% Dichlorobenzene Mass of Sorbent HCP Parathion 1,2-Dichlorobenzene (g ) (%) (%) (%) 15 16 25 0.5 16 13.5 16 * 100% is defined as the amount that will leach from the waste if solidified with fly ash. S tr-xhf »E r* 1 a " " tIf BU E OMPI Example 10 An example of the effect on leaching of organo¬ clays on highly toxic waste can be seen in solidifica¬ tion of a waste obtained from Rocky Mountain Arsenal in Denver, Colorado. The problems associated with these wastes have been widely-known and publicized in the Rocky Mountain area. This waste contained large amounts of industrial by-products and pesticides. This waste was solidified employing 5% by weight of a dimethyl di(hydrogenated tallow) ammonium bentonite organoclay, 30% attapulgite, and 80% cement. The waste was then subjected to the standard EPA extraction procedure. The extract was then analyzed for residues of the host of organics present in the original waste. Gas chromato- - graphic analyses of the leached original waste and the leached solidified product are given in Figure 4. It is clear that the method of this invention greatly re¬ duces the leaching of the organics from this waste. Example 11 Table 13 shows examples of the effectiveness of the organoclays in breaking organic-water emulsions. εuBSTi E SHEET Table 12 Organoclay Applied to Breaking of Organic Water Emulsions Organoclayl Percent of Type of Dose (% of Water Emulsion Composition Composition) Recovered Texaco API Sepa¬ 60% organic 2.5% 98% rator Sludge 40% water Amoco API Sepa¬ 80% organic 2.5% 95% rator Sludge 20% water BFI Hazardous 1/3 solids 2.5% 98% Waste 1/3 organic 1/3 water Alcoa Rolling 10% solids 7% 90% Mill Emulsion 40% organic 50% water 1 Organoclay utilized was a dimethyl di(hydrogenated tallow) ammonium bentonite. * * * Although the invention has been described in conjunction with the foregoing specific embodiments, many alternatives, variations and modifications are intended to fall within the spirit and scope of the appended claims. suesT OMPI

Claims: Claims 1. A method of treating a polar fluid composition con¬ taining an amount of organic contaminant to substan¬ tially immobilize the contaminant to facilitate disposal, comprising: (a) adding a sufficient amount of an organoclay to the fluid composition to absorb substantially all of the contaminant; and (b) adding a sufficient amount of solid adsorbant to adsorb or react with substantially all of the polar fluid to form a substantially non-flowable matrix. 2. A method of treating an aqueous fluid composition containing an amount of organic contaminant to sub¬ stantially immobilize the contaminant to facilitate disposal, comprising: (a) adding a sufficient amount of organoclay to the aqueous composition to absorb substantially all of the contaminent; and (b) adding a sufficient amount of solid adsorbant to adsorb or react with substantially all of the water to form a substantially non-flowable matrix. 3. The method of claim 1 or 2, wherein the fluid compo¬ sition is an emulsion. 4. The method of claim 1, 2, or 3 further comprising, after the step of adding the organoclay, removing a portion of the polar fluid or water. 5. The method of claim 1 or 2, wherein the organoclay is a higher dialkyl dimethyl ammonium organoclay. 6. The method of claim 1 or 2, wherein the organoclay is a benzyl ammonium organoclay. SΠE.≥.T 7. The method of claim 1 or 2, wherein the organoclay is a ethylhydroxy ammonium organoclay. 8. The method of claim 1 or 2, wherein the solid adsorb¬ ent is attapulgite. 9. The method of claim 1 or 2, wherein the solid adsorb¬ ent is cement. 10. The method of claim 1 or 2, wherein the solid adsorb¬ ent is a mixture of attapulgite and cement. 11. The method of claim 1 or 2, wherein the solid adsorb- ent is fly ash. 12. The method of claim 1 or 2, wherein the solid adsorb¬ ent is saw dust. 13. The method of claim 1 or 2, wherein the solid adsorb¬ ent is soil. 14. The method of claim 1 or 2, wherein the solid adsorb¬ ent is kiln dust. 15. The method of claim 1 or 2, wherein the amount of organoclay is at least about 1% by weight of the amount of organic contaminant. 16. The method of claim 1 or 2, wherein the amount of organoclay is at least about 5% by weight of the amount of organic contaminant. 17. The method of claim 15, wherein the amount of organo¬ clay is a maximum of about 10% by weight of the amount of organic contaminant. 7i 3 ϋ a " i Ξ. Sπ 2_.fi. I OMPI W1P0 18. The method of claim 16, wherein the amount of organo¬ clay is a maximum of about 10% by weight of the amount of organic contaminant. 19. The method of claim 1 or 2, wherein the amount of solid adsorbent is from about 10% to about 100% by weight of the organic contaminant. 20. The method of claim 4, wherein the amount of solid adsorbent is from about 20% to about 25% by weight of the organic contaminant after removing a portion of the polar fluid or water. 21. The method of claim 1 or 2, wherein the organoclay and solid adsorbent are added substantially simultan¬ eously to the fluid composition. 22. A substantially non-flowable matrix, comprising: (a) an amount of polar fluid; (b) an amount of organ¬ ic contaminant in the polar fluid; (c) a sufficient amount of organoclay to absorb substantially all of the contaminant; and (d) a sufficient amount of solid adsorbent to adsorb or react with substantially all of the polar fluid to form a substantially non-flow¬ able matrix. 23. A substantially non-flowable matrix, comprising: (a) an amount of water; (b) an amount of organic contaminant in the water; (c) a sufficient amount of organoclay to absorb substantially all of the contam¬ inant; and (d) a sufficient amount of solid adsorbent to adsorb or react with substantially all of the water, to form a substantially non-flowable matrix. SUBSTITUTE SHEET 24. The matrix of claim 22 or 23, wherein the organoclay is a higher dialkyl dimethyl ammonium organoclay. 25. The matrix of claim 22 or 23, wherein the organoclay is a benzyl ammonium organoclay. 26. The matrix of claim 22 or 23, wherein the organoclay is an ethylhydroxy ammonium organoclay. 27. The matrix of claim 22 or 23, wherein the solid ad¬ sorbent is attapulgite. 28. The matrix of claim 22 or 23, wherein the solid ad- sorbent is cement. 29. The matrix of claim 22 or 23, wherein the solid ad¬ sorbent is a mixture of attapulgite or cement. 30. The matrix of claim 22 or 23, wherein the solid ad¬ sorbent is fly ash. 31. The matrix of claim 22 or 23, wherein the solid ad¬ sorbent is saw dust. 32. The matrix of claim 22 or 23, wherein the solid ad¬ sorbent is soil. 33. The matrix of claims 22 or 23, wherein the solid ad- sorbent is kiln dust. 34. The matrix of claim 22 or 23, wherein the amount of organoclay is at least about 1% by weight of the amount of organic contaminant. •£■" ** . I: • fe_.- ; .Oiliϋf IC -_. _ t i'.ξ<_.V___.'_f__.TI 35. The matrix of claim 22 or 23, wherein the amount of organoclay is at least about 5% by weight of the amount of organic contaminant. 36. The matrix of claim 34, wherein the amount of organ- oclay is a maximum of about 10% by weight of the amount of organic contaminant. 37. The matrix of claim 35, wherein the amount of organ¬ oclay is a maximum of about 10% by weight of the amount of organic contaminant. 38. The matrix of claim 22 or 23, wherein the amount of solid adsorbent is from about 10% to about 100% by weight of the organic contaminant. 39. The matrix of claim 22 or 23, wherein the amount of solid adsorbent is from about 20% to about 25% by weight of the organic contaminant. a- Cw._T,i . ._P__-.tJ_-_,*i~

Inventors: BEALL GARY W, BEALL, GARY, W.
Applicants: RADIAN CORP, RADIAN CORPORATION
Application year: 1982
Main classification: B01D15
IPC codes: B01D15, B01J20, B09B1, C02F1, E02D31