JP2002534254A - Methods and compositions for treating substances contaminated with hydrocarbons - Google Patents

Abstract

  (57) [Summary] A composition for treating a material contaminated with a hydrocarbon-based compound comprises a protein component, a bulking agent, and a microorganism culture capable of metabolizing the hydrocarbon contaminant. Mixing the composition with the contaminated material and absorbing or adsorbing the contaminants prevents the contaminants from leaching into the environment. The microbial culture allows for the biodegradation of the contaminant, thereby eliminating any environmental hazards associated with the contaminated material. The protein component and the bulking agent are preferably organic in nature, and the microbial culture may be unique to the protein material. The present invention also provides a method of treating a material contaminated with hydrocarbons using the composition described above. The invention is particularly suitable for treating contaminated drill cutting.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] Background of the Invention 1. TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for treating materials contaminated with hydrocarbonaceous materials, and compositions for such a method. The invention is particularly concerned with oil contamination in drill cuttings caused by drilling of well holes.

[0002] 2. 2. Description of the Related Art Land and water oil pollution is a major environmental problem. There are many instances in which ecosystems are severely damaged by accidental spills of oils or other hydrocarbon compounds.

[0003] One of the places where oil pollution is occurring regularly is in land or sea well drilling systems. In the drilling process, oil-contaminated drill cuttings are carried to the surface and collected. Drill cutting and other materials that are carried to the surface must be treated to remove oily contaminants so that they do not seep into the soil or be dumped in water.

[0004] Various solutions have been proposed to address this problem, such as burning the drill cuttings or cleaning them with a detergent solution. This first method poses safety and environmental hazards. The second method has a long processing time and, depending on the detergent used, may risk further contamination.

[0005] US Pat. No. 4,242,146 teaches a method for treating oil-contaminated drill cuttings coming from offshore drilling rigs. In this patent, any free oil is removed by contacting the contaminated drill cutting with an oil absorbing material such as clay. Next, the drill cutting and the absorbent are combined and returned to water. This reference does not teach how to remove oil contaminants other than simply absorbing and releasing oil from drill cutting.

[0006] Various other references teach methods for treating oil pollution in water bodies. U.S. Pat. No. 4,925,343 teaches a composition for cleaning oil contamination comprising a particulate mixture of wood fibers and a hydrophobic cotton long fiber material. Similar methods are taught in U.S. Patent Nos. 4,061,567 and 3,617,564. These references teach the use of synthetic or natural fibers to absorb hydrocarbon contaminants from water or land.

[0007] Although these references address oil pollution, they do not address the decomposition of hydrocarbon contaminants to completely eliminate the risk of contamination.

[0008] US Pat. No. 5,395,535 teaches a method of removing carbohydrate-based materials from water or land, comprising spraying dry plant or vegetable components throughout the contamination. The "trash" or waste of the gin is indicated as the material used in this method. This cotton material is spread throughout the oil contamination to absorb and retain the contaminants. The material containing the absorbed oil is then fermented, wherein the indigenous bacteria of the cotton material biodegrade the carbohydrate contaminants.

[0009] US Pat. No. 5,635,392 also teaches a method for treating oil-contaminated materials that removes contaminants using the action of microorganisms. This reference teaches, along with the microbial inoculum, a nutrient mixture to be added to hydrocarbon contaminated materials to stimulate the growth of the culture. As such, contaminants are removed from the system.

[0010] The latter two references deal with the removal of contaminants, but such biodegradation is time consuming and may spread before the removal is complete.

Therefore, there is a need for an efficient method for removing hydrocarbon pollution in water or on land, as well as a method for achieving such removal while minimizing any leaching of contaminants. Accordingly, the present invention provides a means for on-site containment and treatment of drilling residues. A means for on-site stabilization and immobilization of leachable hydrocarbons using only organic sorbents. The present invention provides a means for in-situ bioremediation of hydrocarbons by biodegradation.

[0012] SUMMARY OF THE INVENTION Accordingly, provided in one embodiment, the present invention is a protein component and a bulking component (bulking agents, bulking component) and comprises a composition for treating contaminated material with a hydrocarbon I do.

In another embodiment, the present invention provides a treatment composition comprising a hydrocarbon-contaminated material comprising a protein component, a bulking agent, and a microbial culture capable of metabolizing hydrocarbon contaminants. A method of treating, comprising: 1) contacting the material with the treating composition to immobilize hydrocarbon contaminants;
And 2) biodegrading the contaminant with the microorganism culture.

[0014] These and other features of the preferred embodiments of the present invention will become more apparent in the following detailed description, with reference to the accompanying drawings.

[0015] The preferred hydrocarbon contaminants by Description invention embodiments, essentially organic, comprising any liquid contaminant is leachable and hydrophobic, and as gasoline, oil, etc. creosote . Such contaminants can be seen as spills on water or on land contaminated by such liquid contaminants or in soil material (ie, trash, clay, shale, drill cutting, etc.). As an example, the invention will be described for drill cutting. However, it will be appreciated that the invention may have various applications.

As noted above, desirable features of such a method for treating hydrocarbon contaminants are the rate of contaminant removal and efficient decomposition. Thus, the present invention provides, in one embodiment, a treatment composition for treating materials contaminated with hydrocarbon contaminants as described above, whereby such contaminants are safely removed by biodegradation. provide. The composition of the present invention contains a protein component and a bulking agent as active ingredients. In a preferred embodiment, the protein component and the bulking agent are organic in nature.

The treatment composition according to a preferred embodiment of the present invention is characterized by the following capabilities:

The ability to build a primary organic matrix; to develop, maintain and / or maintain a native or artificially inoculated microbial consortium capable of metabolizing hydrocarbon contaminants to acceptable limits. Or the ability to promote; the ability to prevent the detrimental movement (ie leaching) of contaminants when placed in a biopile or spread over soil surfaces in the presence or absence of water; Ability to spread on or below the surface of unsoiled soil and to protect the oil-free integrity of the soil received at the time of spreading or uptake or at any time thereafter.

In a preferred embodiment, the protein components of the composition serve a variety of purposes. First, the protein component provides a source of endemic microorganisms with the biodegradability of hydrocarbon contaminants. Second, the protein component serves as a source of nutrients for the microorganisms performing the biodegradation process. In another embodiment, the required microorganism is added to the treatment composition to provide the required microbial culture contained in the protein component, or to supplement or complete the culture. May be included. Whether the protein component provides a source of microorganisms depends on the choice of protein material. For example, it has been mentioned above that cotton fiber waste provides a unique source of hydrocarbon-consuming microorganisms. Similar proteinaceous microbial sources may also be used.
For example, suitable sources of the protein component of the present invention include canola (or rapeseed), soy, cotton, corn or peanut material, or other protein-based materials, or any combination thereof. Usually, the protein component comprises an organic protein powder.

Another preferred feature of the protein component is its ability to absorb or adsorb hydrocarbon contaminants. This sorption capacity serves to immobilize the hydrocarbons and thereby prevent leaching of such compounds from a containment mix (combination of contaminated material and treatment composition).

Accordingly, the protein component of the present invention is characterized by the following abilities.

The ability to exhibit sorption capacity for a range of hydrophobic organic contaminants; the ability to act as a lipophilic sorbent (preferably for oil in the presence of water); during the compounding / mixing process Ability to remove (immobilize) free liquid contaminants on and after being sprayed on the ground; ability to provide a source of elemental nitrogen in the form of proteins; bulk of liquid contaminants or contaminated substrates Ability to alter density; Ability to provide a source of endemic microorganisms capable of metabolizing hydrocarbon contaminants; Ability to be readily available and available in large quantities; Stable, non-phytotoxic or non-microbial toxic Some ability.

As mentioned above, the bulking agent is preferably essentially organic. The bulking agent may include, for example, wood shavings, peat moss, straw, and the like, or any combination thereof. The primary function of the bulking agent is to build a structure within the containment mixture, and secondly, to provide additional absorbency for contaminants.
Such a structure provides efficient gas or air exchange properties. This is important. This is because the biodegradation process requires aerobic conditions to maintain the desired increased level of microbial activity. Such conditions increase the efficiency of biodegradation, which is important when dealing with hydrocarbon contaminants.
One bulking agent or a combination of several can be used. Ideally, the bulking agent is selected for its ability to reduce the overall bulk density of the containment mixture and to provide appropriate conditions for microbial activity.

In another embodiment, the present invention provides a method of treating a material contaminated with hydrocarbons using the composition described above. In a first step, the method immobilizes and stabilizes contaminants in a homogeneous containment mixture. This is achieved by contacting the contaminated material with the treatment composition of the present invention described above. Such contact can be achieved in several ways, such as by mechanical or physical compounding or mixing. This contacting step achieves homogeneity (immobilization of the contaminants) at the macroscopic level as well as at the microscopic level; if necessary, diluting the contaminants with the treatment composition and other additives; Intended to achieve the desired contaminant immobilization and bulking by the ability to adjust the volume of the application composition; to stimulate or enhance microbial inoculum and / or microbial activity in the containment mixture Additives [eg fertilizers, bionutrients (bi
onutrient), sustained release oxygenator, bioaugmentati
on agents), hydrocarbon washes / chain scissors, etc.) into the mixture.

In addition, the compounding or mixing step may comprise dissolving soluble salts from the contaminated material,
Metals and other analytes are "washed out" or "dissolved" to provide the opportunity to alter the electrical conductivity, sodium adsorption and pH of the resulting containment mixture.

An immobilization step is used to prevent or reduce any leaching of contaminants. Such leaching can be accomplished using Toxicity Characteristic Leaching Procedu
re; TCLP), which is a standardized leaching assay approved by the regulatory body. It is designed to measure the mobility of both organic and inorganic analytes present in liquid, solid and multiphase wastes. The test is carried out as follows: for waste containing more than 0.5% solids, a minimum of 100 g of solid phase sample is mixed with a volume of water equal to 20 times the weight of the solid phase. In this case, the water is called the extract. Typically, the water must be purified, deionized, and organic-free. When preparing samples, the size of the solid
If it is larger than 9.5 mm, grinding, grinding and cutting are required. The mixture is placed in a specialized bottle-shaped extraction container (minimum volume 2 L). Next, the container is placed in a stirring device. The stirrer allows the container to be moved in an end-over-end fashion for 30 minutes.
Spin at rpm for 18 hours. After stirring, pour the mixture into a 0.6-0.8 μm glass fiber filter. The leachate is collected and analyzed for the presence of hydrocarbons.

After the immobilization step, the microbial activity in the containment mixture (ie, the mixture of the contaminated material and the treatment composition and any other additives) is sustained, whereby hydrocarbon contaminants are removed. Biodegradable. As mentioned above, the source of microorganisms for the biodegradation step may be native or introduced. Protein components and bulking agents make up the main source of endemic microorganisms. Further, in another embodiment, a fertilizer, sewage sludge, or any other microbial active liquid or soil is used to introduce, during or after mixing, natural microorganisms capable of metabolizing hydrocarbons into the containment mixture. be able to. It is also possible to introduce additional microorganisms into the containment mixture during or after the mixing of the active substances, using a genetically synthesized microbial inoculum or culture.

With the present invention, hydrocarbon contaminants are safely disposed of without further processing, while limiting or preventing leaching of the contaminants during biodegradation.

As mentioned above, the present invention has been described in relation to the treatment of contaminated cuttings. However, the methods and compositions of the present invention are equally applicable to other materials that have been exposed to oil or hydrocarbon contamination on land or in water.

The following examples and tests illustrate the advantages of the present invention, but are not intended to limit the invention.

1) Rooftop Leaching Test A specialized rooftop leaching tray (Roof-Top Leach Tray) was designed to examine the hydrocarbon immobilization and stabilization capabilities of the treatment mixture. The purpose is to develop a test
The aim is to develop tests to provide analytical evidence that the petroleum hydrocarbons in the sample remain fixed and retain resistance to leaching. A description of each sample or mixture (tested for nine) is provided in the results below.

The mixing ratio is expressed as the percentage of canola flour required to treat a specified amount of drilling residue. It is measured using the Agitation / Filtration Test. The purpose is to determine if sufficient canola flour (acting as an oil absorbent) is present in the treatment mixture to effectively fix all petroleum hydrocarbons associated with the treatment mixture That is. The procedure of the stirring / filtration test is as follows.

1) Put the processing mixture in a sealed container. Water is added at a rate of 5 parts solution to 1 part solid (residue) according to the following calculation: Conversion: 500 mm annual precipitation on average in the area with a maximum depth of 10 cm (100 mm) Therefore, the conversion is 500: 100 for water to mixture (corresponding to 5: 1).

2) The container is sealed and forcibly stirred for about 2 minutes. While the solids are suspended, the contents of the vessel are filtered through a funnel with a fine mesh sieve. The filtrate is collected in a clear container and analyzed for the presence of oily luster on the surface. If present, gloss is an indicator that the mixing ratio used is not effective to completely fix the hydrocarbon component of the particular mixture.

3) Subsequently, it is necessary to mix the additives and retry.

The roof leaching tray is designed similar to that of a steeply sloping roof (30% slope) for worst case simulation. A total of 20 L of the sample mixture is sprayed on each side of the infusion tray (having dimensions of 45 cm × 45 cm or 20 cm × 20 cm) up to a maximum thickness of 10 cm. The mixture is held in place by a screen that prevents the transfer of solids but allows water to flow freely. Precipitation and runoff
Water is sprayed on the mixture to simulate the conditions of off).

While this design may be considered an exaggeration of extreme conditions and extreme conditions, the purpose is to move water quickly across the cross-section of the mixture to pass through it. To "wash out" poorly absorbed or excess hydrocarbons. All excess water was collected as leachate in a collection tray equipped with a drain plug. The leachate was analyzed for the presence of petroleum hydrocarbons, as indicated by the luster of the oil, or sampled for laboratory analysis.

Since the results of the preliminary test were favorable, the above two tests: 1) stirring /
Hydrocarbon immobilization was tested using filtration tests and 2) toxic leaching (TCLP).

Leach Test Results The following are the results of analytical tests on samples from the above filtration and leaching tests. A total of nine samples were analyzed. These samples correspond to leachates, filtrates and solids across a range having various total petroleum hydrocarbon (TPH) values.

What follows is a summary of sample descriptions, TPH test results, and commentary on the results.

[0041] The following table summarizes the above results.

[0042] Discussion The purpose of the above analytical tests is to determine how efficiently rapeseed flour (canola flour) and shavings can be carbonized using the presence or absence of detectable hydrocarbons in liquids and solids after leaching or filtration. It was to show if hydrogen could be fixed. Under similar conditions, the leachate and filtrate hydrocarbon concentrations are inversely proportional to the amount of fixed hydrocarbons. As expected, the highest hydrocarbon concentration (8.7%) appeared in the intact (untreated) residue sample. This value is the average retort result of 14% (average retort r
esults) is somewhat conservative. This difference is due to the hog fuel
l) It appears to be caused by dilution caused by the varying amounts of cellulose between samples due to the components.

Mixing Ratio When the residue is treated with rapeseed flour at a ratio of 4: 1 (by volume) or 7: 1 (by weight), despite the fact that many different mixing ratios were first tested with various achievements. Provided favorable results, and therefore were used as the target mix ratio for further analytical tests. In addition, the results from the mixing ratio of 2 parts by weight of the residue (or 3.5 to 1 (by weight)) with respect to 1 part by weight of rapeseed flour are also tested, as a comparison standard and for the absorption treatment of petroleum hydrocarbons. When rapeseed powder was used as an agent, an index was obtained as to whether or not the amount was better. Comparison of the results from Samples 5 and 8 shows that apparently less rapeseed powder is better than more in that the filtrate of Sample 5 has significantly less TPH than that of Sample 8. It is. However, differences in the concentration of hydrocarbons and the amount of hog fuel in these two samples prior to mixing may also have contributed to the difference. In any case, this difference is negligible since it is well below the imposed limit (1000 ppm or 0.1%).

[0044] In most cases duration, sampling was conducted after those corresponding to precipitation event of the maximum intensity of only 4 times and 8 times. The leachate generated during this apparently short time frame,
It is expected to reflect a biased concentration of hydrocarbons in the solution due to hydrocarbon "wash-out". Predictably, the leachate produces higher than normal concentrations of hydrocarbons, as excess or poorly absorbed hydrocarbons are initially "washed out" or released from the mixture. Therefore, all values can be considered the largest.

TPH Test Constraints Although the TPH test is widely used as an accurate analysis of the presence of petroleum hydrocarbons, it has one limitation. The TPH or MOG (mineral / oil / grease) test is non-selective. It is composed of lighter aromatics (hydrocarbon rings) and heavier aliphatics (
(Hydrocarbon chains) between different types of petroleum hydrocarbons. However, the TPH test analysis is sufficient for explanation as the present invention relates to the fixation of all petroleum hydrocarbons present in drilling residues.

2) Biodegradation Tests The following tests were performed to evaluate the effect of various additives to the treatment mixture on hydrocarbon biodegradation for on-site drilling waste treatment and disposal. The additives tested were as follows:

[0047] 1. Reactivated sludge (RAS) from a sewage treatment plant in the city of Calgary, intended to provide the first bacterial inoculum with potential hydrocarbon resolution.

[0048] 2. Biocat 4000-An organic and inorganic liquid nutrient source intended to provide a complete nutrient source to support microbial growth and hydrocarbon biodegradation activity.

[0049] 3. Percarbonate (OX); a solid oxygen releasing compound intended to provide more oxygen for faster biodegradation rates.

This test was performed at room temperature for 6 weeks (41 days) without mixing to evaluate the effect of the various additives above on the control (no additive) in promoting the rate of hydrocarbon biodegradation. did.

[0051] were tested the following sample method.

A) One 20 L bucket containing compost mixture (oil shavings, wood chips and canola flour).

Note: The bucket had a strong pungent odor and was sealed and apparently anaerobic during transport and storage.

B) One 500 ml glass bottle containing a sustained release oxygen compound (fine white powder)
Four 1L glass bottles of reactivated sludge (RAS). These were kept anaerobic because they smelled when empty. All bottles were placed in 10 L containers and aerated overnight to return to aerobic conditions to ensure RAS growth.

C) Biocat 4000 containing 70% organic nutrient base + 30% inorganic nutrient base
One 4L plastic jugg.

[0056] To each of the four 6 L reactors (with removable gasket-sealed lids), 4 L of the processing mixture was added. The various additives tested were as follows.

[0057] All 4 L test mixtures were mixed thoroughly by hand in an 8 L vessel before being placed in the 6 L reactor. Soil moisture probes indicated that all mixtures were wet, but there was no free, stagnant water. Each test mixture was sampled (200 ml) for the next initial analysis.

-PH-conductivity, EC (dS / m)-moisture content (wt%)-total heterotrophic bacteria (THB) by the most probable number (MPN) (MPN / g for 48 hours) -MPN by hydrocarbon degrading bacteria (HDB) (14 days MPN / g) - total extract hydrocarbons (by _{TEH C 8 ~C 30, GC /} FID analysis) (mg / kg) - available nutrients (N , P, K, S) (mg / kg)-Total nitrogen (TKN) by Kjeldahl method (wt%) All reactors were incubated at room temperature, but the room temperature was varied between 19 and 24 ° C. The surface of each reactor was exposed to room light for about 8 hours per day.

At regular intervals, a gasket-sealed lid was placed on the reactor, and the oxygen uptake rate and carbon dioxide generation rate were recorded. After determining the respiration rate, the lid was removed to ensure continuous passive ventilation of the mixture. No further mixing was performed to evaluate the possibility of passive diffusion of air from the surface. At the start and end of the test, the depth of each test mixture in the reactor was recorded to determine the degree of compression after vigorous degradation.

Results and Discussion This test was performed for 41 days. The analysis results on days 0 and 41 are summarized in the table below.

[0061] The initial mixture contained about 114,600 mg / kg of total extracted hydrocarbons. This is shown in FIG.
This figure shows that the total extracted hydrocarbons from the initial mixture on day 0 of the test (
The mass fraction of TEH) is shown relative to the residual TEH from each test after 41 days. Only about 3% of TEH was C30 + material.

Test 1--Control The control was the same as the initial mixture, but received enough water to support good biological activity. Overall, it can be seen that this control produced the best hydrocarbon cracking results.

[0063] Composting activity was revealed by an increase in temperature in the test mixture from day 5 to day 26. The test mixture retained 92% of its initial depth after 41 days.

In the control, the initial bacterial count was higher than expected (1.3 × 10 ⁹ MPN / g), which provided the native bacterial inoculum with a mixed nitrogen source, wood shavings and / or cuttings. Suggest that it would have been The initial number of hydrocarbon-degrading bacteria was very low (7.9 × 10 ² ), indicating that the group was not yet compatible with the hydrocarbon content. It should also be noted here that no significant development of white rot fungi was observed in any of the test mixtures, unlike reports from field observations during composting of the mixture without additives. is there.

The control mixture showed the highest degree of hydrocarbon biodegradation (85% based on one combined sample analysis). 2 and 3 show the results of GC / FID analysis of residual hydrocarbons in the range C8-C30 compared to the initial hydrocarbons present on day 0. A negative change in the residual hydrocarbon mass fraction indicates that the fraction is less than the initial hydrocarbon. Loss of both light hydrocarbons (C8-C11) and heavy hydrocarbons (C21-C30 +) indicates that biodegradation has occurred. Some of the C8-C11 loss appears to be due to volatilization during the preparation of the additive-containing test mixture. An apparent increase in hydrocarbons in the C12-C20 range occurs to bring the mass fraction to a total of one. Some of the heavy fractions
It may be broken down into smaller hydrocarbons in the C12-C20 range.

Analysis of nutrients showed that no nutrients would limit the study for the next 41 days. Although the test mixture was sprayed with water periodically, the moisture content was
Down to 1/2. At the end of this test, the moisture content in the top 3/4 of the test mixture was only 9.1 wt% and in the bottom 1/4 it was 35.4 wt%.

The low amount of water present at the end of the test, as shown in FIGS. 4 and 5, explains the reduction in respiratory activity after day 13. Since there was no mixing during the test, it was difficult to ensure that adequate moisture was maintained throughout the test mixture. In all tests, a clear layer separation of the water was seen, where the bottom was wet and the top was dry.

With a continuous supply of water, the leachate collects at the bottom of the reactor, which creates anaerobic conditions. Future tests should use a reactor with a leachate drain so that more water can be added throughout the test.

Test 2-RAS only composting activity was demonstrated by an increase in temperature in the test mixture from day 5 to day 26. The test mixture retained 87% of its initial depth after 41 days.

As expected, the addition of regenerated activated sludge (RAS) increased the initial bacterial count, although
> 10 ¹¹ MPN / g), the effect was not very pronounced due to the high initial number in the initial mixture. The initial number of hydrocarbon-degrading bacteria was still low (1.3 × 10 ³ ), indicating that the number of hydrocarbon-degrading microorganisms in RAS was not high.

The sample containing only the RAS additive showed the second highest degree of hydrocarbon biodegradation (48% based on one combined sample analysis). FIG. 2 shows the results of GC / FID analysis of residual hydrocarbons in the range C8-C30 compared to the initial hydrocarbons present on day 0. Similar to the results of Test 1, light hydrocarbons (C8 to C11) and heavy hydrocarbons (C21 to C30 +
), Together with positive respiratory data, indicate that biodegradation is occurring. Some of the C8-C11 loss appears to be due to volatilization during preparation of the test mixture.

Analysis of nutrients showed that no nutrients limit the test for the next 41 days. Unlike test control, the RAS additives, high ammonia content occurs in the test mixture until day 41 _{(1700mg / kg NH 4 -N)} . This may have been caused by the degradation of a portion of the RAS bio-solid and release of ammonia by deamination of the protein. This level of ammonia can be toxic to some bacteria. The number of heterotrophic bacteria was still high (> 10 ¹¹ MPN / g), indicating that no significant bacterial killing had occurred. The number of hydrocarbon degrading bacteria did not increase or remained viable until day 41.

Despite the regular spraying of water on the surface of the test mixture, the water content dropped to about 1/2 of the original. At the end of this test, the moisture content in the top 3/4 of the test mixture was only 9.4 wt%, while in the bottom 1/4 it was 39 wt%.

The low moisture present at the end of the test is shown in FIGS. 4 and 5.
It explains the decline in respiratory activity after day 13. This also explains the low number of hydrocarbon-degrading bacteria.

Test 3-RAS + Biocat 4000 Composting activity was revealed by an increase in temperature in the test mixture from day 5 to day 26. Trial 3 showed the highest sustained temperature rise, indicating the highest biological activity. The test mixture retained 92% of its initial height after 41 days.

Although not analyzed directly, the addition of reactivated sludge (RAS) should have increased the number of early vegetative heterologous bacteria, as in Test 2. Since Biocat 4000 contains no living bacteria (not confirmed in this test), the number of initial carbohydrate-degrading bacteria would also be similar to Test 2.

The RAS + Biocat 4000 additive showed the third highest degree of hydrocarbon biodegradation (39%
, Based on one combined sample analysis). FIG. 2 shows the results of GC / FID analysis of residual hydrocarbons in the range C8-C30 compared to the initial hydrocarbons present on day 0. It was observed that more light hydrocarbons (C8-C11) were lost and less heavy hydrocarbons (C22 only) were lost. The change in hydrocarbons from this initial one indicates that biodegradation has occurred, but to a lesser extent than in Tests 1 and 2. As noted above, some of the C8-C11 loss appears to be due to volatilization during preparation of the test mixture. Biocat 4000 may also have introduced some plant-based organics that appear in the GC / FID analysis as hydrocarbons ranging from C15 to C30 +, which have not yet been analyzed.

Analysis of the nutrients indicated that no nutrients restricted the study for the next 41 days. In the same manner as in Test 2, the RAS additives, high ammonia content occurs in the test mixture until day 41 _{(1780mg / kg NH 4 -N)} . The number of heterotrophic bacteria was still high (> 10 ¹¹ MPN / g), indicating that no significant bacterial killing had occurred. The number of hydrocarbon-degrading bacteria was increased compared to Test 2, but was still low at day 41.

The moisture content dropped to about 1/2 of the initial, despite the regular spraying of water on the surface of the test mixture. At the end of this test, the moisture content in the top 3/4 of the test mixture was only 9.6 wt%, while in the bottom 1/4 it was 38 wt%.

Test 3 had the highest overall respiration rate, which is consistent with the highest temperature seen in this test mixture. The low amount of water present at the end of this test explains the decrease in respiratory activity after day 13, as shown in FIGS. This also explains the low number of hydrocarbon-degrading bacteria.

Test 3 showed the highest apparent biological activity, but the reduction in residual TEH was only the third highest. This means that the RAS additive introduces a greater number of bacteria in the initial mixture that are more compatible with degrading wood shavings (cellulose hydrolytic activity) and decomposing organic nitrogen sources than hydrocarbons, and that the Biocat 4000 Probably the result of being stimulated by

Test 4-RAS + Biocat 4000 + Percarbonate Oxygen Release Compound (OX) Composting activity was revealed by an increase in temperature in the test mixture from day 5 to day 26. The test mixture retained 87% of its initial height after 41 days.

The most notable difference in this test is the pH as high as 9.4, which was caused by the addition of percarbonate. The initial pH increased from about 7.7 to 9.1 with the addition of 1 vol% of percarbonate. This high pH has an inhibitory effect on the activity of the bacteria.

Although not analyzed directly, the addition of regenerated activated sludge (RAS) should have increased the number of initial heterotrophic bacteria, as in tests 2 and 3. The number of initial carbohydrate-degrading bacteria would also be similar to tests 2 and 3.

The RAS + Biocat + OX additive showed the lowest degree of hydrocarbon biodegradation (25%,
Based on one combined sample analysis). FIG. 2 shows the results of GC / FID analysis of residual hydrocarbons in the range C8-C30 compared to the initial hydrocarbons present on day 0. Test 3
As with more light hydrocarbons (C8-C14) are lost and heavy hydrocarbons (C22 only)
Was observed to be less lost. The change in hydrocarbons from this initial one indicates that biodegradation has occurred, but to a lesser extent than in Tests 1 and 2. Some of the C8-C11 loss appears to be due to volatilization during preparation of the test mixture. Biocat 4000 may also have introduced some plant-based organics that appear as hydrocarbons ranging from C15 to C30 + in GC / FID analysis, but this has not been measured.

Analysis of the nutrients showed that no nutrients limit the test for the next 41 days. In the same manner as in Test 2 and 3, the RAS additives, high ammonia content occurs in the test mixture until day 41 _{(1350mg / kg NH 4 -N)} . Heterotrophic bacterial counts were lower than in other tests (2.3 × 10 ⁶ MPN / g), indicating that significant bacterial killing had occurred. The number of hydrocarbon-degrading bacteria was also very low on day 41.
This lower bacterial count is almost certainly due to the higher pH of the test mixture compared to the other tests.

Despite the regular spraying of water on the surface of the test mixture, the water content dropped to about 1/2 of the original. At the end of this test, the moisture content in the top three-quarters of the test mixture was only 10.3 wt%, while in the bottom quarter it was 37 wt%.

Test 4 had the lowest overall respiration rate, which is consistent with the lowest temperature seen in this test mixture. The low amount of water present at the end of this test explains the decrease in respiratory activity after day 13, as shown in FIGS.

Conclusions • Regenerated activated sludge (RAS) did not provide a compatible carbohydrate-degrading bacterium, and appears to have introduced an antagonistic cellulolytic activity, but the latter possibility needs further confirmation. .

Degradation of RAS biosolids results in very high ammonia-nitrogen contents exceeding 1300 mg / kg, which is likely to be toxic to hydrocarbon degrading bacteria.

• Biocat 4000 promoted activity in Test 3, but did not result in increased hydrocarbon cracking results.

• The percarbonate solid oxygen releasing compound produced an initial pH as high as 9.1, which resulted in low microbial activity, as indicated by respiration and temperature results.

The treatment mixture (control) appears to be fairly well balanced, with bacterial,
Even without additives such as nutrients or oxygen, it supported good microbial activity and rapid hydrocarbon degradation. After 41 days of treatment, still appropriate total nitrogen (0.
87%) and phosphoric acid (78 mg / 4).

• After 41 days, the height of the test mixture is all maintained at 87-92%, which means that the processing mixture is not easily compressed during composting, so that its porosity and passive This indicates that the possibility of ventilation is maintained.

• The treatment mixture tends to dry out over time as the water is drained down. The mixture readily accepts additional water (ie, is not hydrophobic despite high initial hydrocarbon content).

• Based on the findings obtained in this test, maintaining moisture content is a limiting factor in maintaining rapid hydrocarbon biodegradation activity.

• Before citing the findings from this study, the initial and final TEH analysis should be repeated to give an indication of the reliability of the data. This is necessary because at the level at which hydrocarbons are analyzed, there is a certain amount of variation even in mixtures such as those described above.

3) Bioremediation Field Plot A test to determine the effectiveness of using a combination of canola flour and dry wood shavings to contain and biodegrade oily drilling residues in a homogeneous mixture. Was done. The main objective is to gather analytical data from laboratory and field applications to characterize the field treatment (mixing) and land application methods of the present invention.

Thirty field plots were set up at the University of Alberta Ellerslie Field Research Facility, located south of Edmonton, Alberta, Canada. Typical excavation site conditions were simulated by removing organic topsoil from each 3m x 5m plot.

Results FIGS. 6 and 7 show the results of the field test described above.

From the in-field results over 107 days, the invert-based (inver
In the case of containment mixtures, the total rate of hydrocarbon loss under field conditions is as high as 57%, with salt-free containment mixtures in which minimal leaching is limited to 2.5 cm above the lower soil. Showed that it was 37%.

As noted above, the invention has been described with particular reference to the use of canola (or rapeseed) flour as a protein source, but a variety of other sources are possible. Some examples are: cottonseed flour, soy flour, alfalfa flour, bone flour, blood flour, feather flour, kelp flour, peanut flour, borage flour, corn flour, coconut flour,
Sesame flour, safflower flour, sunflower flour, hemp flour and sugar beet flour. One skilled in the art will appreciate that any other similar protein source can be used in the present invention.

Although the invention has been described in terms of particular embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention as outlined in the claims herein. It will be clear to you.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE FIGURES FIG. 1 shows day 0 and day 0 under various additive conditions in the biodegradation test.
FIG. 4 shows the total extracted hydrocarbon mass fraction profile on day 41. FIG.

FIG. 2 shows the change in total extracted hydrocarbon mass fraction after 41 days under various additive conditions in a biodegradation test.

FIG. 3 shows the change in initial total extracted hydrocarbon mass fraction after 41 days under control additive conditions in a biodegradation test.

FIG. 4 shows the oxygen uptake rate under various additive conditions in a biodegradation test.

FIG. 5 shows carbon dioxide generation rates under various additive conditions in a biodegradation test.

FIG. 6 shows hydrocarbon reduction during a bioremediation field plot test.

FIG. 7 shows hydrocarbon reduction during a bioremediation field plot test.

[Procedural Amendment] Submission of translation of Article 34 Amendment

[Submission date] March 5, 2001 (2001.3.5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Contents of correction]

[Claims]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72 Inventor Laurel, Ali Canada Tea 2 Jay 4 Y 3 Alberta, Calgary, Lake Ontario Place South East 344 F Term (Reference) 4B065 AA01X AA57X BA22 BD39 BD41 BD43 CA54 CA56 4D004 AA32 AB05 AC07 CA01 CA47 CC08 CC15 CC20

Claims (12)

[Claims] 1. A composition for treating hydrocarbon-contaminated materials, comprising a protein component and a bulking agent. 2. The composition according to claim 1, wherein the protein component is derived from an organic material. 3. The composition according to claim 2, wherein the protein component comprises a protein powder. 4. The composition of claim 3, wherein the protein flour is derived from canola, soy, cotton, corn or peanut material, or from other protein-based materials. 5. The composition of claim 1, wherein the bulking agent is derived from an organic material or an inorganic equivalent. 6. The composition according to claim 5, wherein the bulking agent is selected from wood shavings, peat moss, straw or any combination thereof. 7. The composition according to claim 1, wherein the protein component has an ability to absorb or adsorb hydrocarbon contaminants. 8. The composition according to claim 1, further comprising a microorganism culture capable of metabolizing hydrocarbon contaminants. 9. The composition according to claim 8, wherein the microorganism culture is contained in the protein component. 10. A method of treating a hydrocarbon contaminated material with a treatment composition according to claim 9, comprising: 1) contacting the contaminated material with the treatment composition; The above method comprising the steps of: immobilizing the contaminant to prevent leaching thereof; and 2) biodegrading the hydrocarbon contaminant with a microorganism culture. 11. A method for treating a hydrocarbon-contaminated material using a treatment composition comprising a protein component, a bulking agent, and a microorganism culture capable of metabolizing hydrocarbon contaminants, The above method comprising: 1) contacting the material with the treatment composition to immobilize the hydrocarbon contaminant; and 2) biodegrading the contaminant with the microorganism culture. 12. The method of claim 11, wherein the contacting step comprises mixing or compounding the contaminated material and the treatment composition.