Adsorption Material and Method for Treating Pollutants
20220355269 · 2022-11-10
Assignee
Inventors
- Warren CHUNG (Calgary, CA)
- Xuebing LI (Qingdao, CN)
- Pei YU (Qingdao, CN)
- Mengtao CUI (Qingdao, CN)
- Quan SHI (Beijing, CN)
- Zhiming XU (Beijing, CN)
- Suoqi ZHAO (Beijing, CN)
- Chunming Xu (Beijing, CN)
- Keng H. CHUNG (Edmonton, CA)
Cpc classification
C02F3/345
CHEMISTRY; METALLURGY
C02F3/348
CHEMISTRY; METALLURGY
Y02W10/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J20/26
PERFORMING OPERATIONS; TRANSPORTING
B09C1/10
PERFORMING OPERATIONS; TRANSPORTING
C02F2103/007
CHEMISTRY; METALLURGY
C02F2103/34
CHEMISTRY; METALLURGY
International classification
B01J20/26
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28
PERFORMING OPERATIONS; TRANSPORTING
B09C1/10
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A method of treating or remediating contaminated material, such as water or soil, comprises contacting such material with asphaltenes. The asphaltenes are preferably produced as a by-product of petroleum refining and, in particular, a by-product of vacuum residua. An adsorbent material comprising such asphaltenes is also provided.
Claims
1. An adsorbent material for removing contaminants from contaminated material, wherein the adsorbent material comprises asphaltenes.
2. The adsorbent material of claim 1, wherein the contaminants are organic contaminants.
3. The adsorbent material of claim 1, wherein the asphaltenes are in the form of granules and/or fibers.
4. The adsorbent material of claim 1, wherein the asphaltenes are combined with one or more cultures of microorganisms.
5. The adsorbent material of claim 1, wherein the asphaltenes are in the form of fibers and wherein the adsorbent material is in the form of a mat or a packing.
6. The adsorbent material of claim 1, wherein the asphaltenes are petroleum asphaltenes.
7. The adsorbent material of claim 1, wherein the asphaltenes are raw petroleum asphaltenes obtained from vacuum residua of a petroleum refining process.
8. The adsorbent material of claim 1, wherein the asphaltenes are immobilized by a retainer.
9. An adsorbent material for removing organic contaminants from contaminated material, wherein the adsorbent material comprises asphaltenes; wherein the asphaltenes are raw petroleum asphaltenes obtained from vacuum residua of a petroleum refining process.
10. The adsorbent material of claim 9, wherein the raw petroleum asphaltenes are in the form of granules and/or fibers.
11. The adsorbent material of claim 8, wherein the raw petroleum asphaltenes are combined with one or more cultures of microorganisms.
12. The adsorbent material of claim 9, wherein the raw petroleum asphaltenes are combined with one or more cultures of microorganisms.
13. The adsorbent material of claim 8, wherein the raw petroleum asphaltenes are in the form of fibers and wherein the adsorbent material is in the form of a mat or a packing.
14. The adsorbent material of claim 9, wherein the raw petroleum asphaltenes are in the form of fibers and wherein the adsorbent material is in the form of a mat or a packing.
15. The adsorbent material of claim 10, wherein the raw petroleum asphaltenes are in the form of fibers and wherein the adsorbent material is in the form of a mat or a packing.
16. The adsorbent material of claim 11, wherein the raw petroleum asphaltenes are in the form of fibers and wherein the adsorbent material is in the form of a mat or a packing.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0017] The features of certain embodiments will become more apparent in the following detailed description in which reference is made to the appended figures wherein:
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
[0024]
[0025]
[0026]
DETAILED DESCRIPTION
[0027] The terms “comprise”, “comprises”, “comprised” or “comprising” may be used in the present description. As used herein (including the specification and/or the claims), these terms are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not as precluding the presence of one or more other feature, integer, step, component or a group thereof as would be apparent to persons having ordinary skill in the relevant art. Thus, the term “comprising” as used in this specification means “consisting at least in part of”. When interpreting statements in this specification that include that term, the features, prefaced by that term in each statement, all need to be present but other features can also be present. Related terms such as “comprise” and “comprised” are to be interpreted in the same manner.
[0028] The term “and/or” can mean “and” or “or”.
[0029] Unless stated otherwise herein, the article “a” when used to identify any element is not intended to constitute a limitation of just one and will, instead, be understood to mean “at least one” or “one or more”.
[0030] The present description utilizes the unique properties of petroleum asphaltenes, which are solid by-products of the solvent deasphalting process, for the effective treatment of water and soil as well as other similar contaminated materials. Thus, in one aspect, the present description provides a use of asphaltenes for the treatment of contaminated water, soil, other similar material. In a particular aspect, the subject asphaltenes described herein are petroleum asphaltenes, such as those produced by a process described in U.S. Patent No. 7,597,794 referred to above. The scope of the present description is not limited to the source or production means of the asphaltenes.
[0031] While asphaltenes may contain substantial amounts of contaminants (metals, sulfur, nitrogen, and coke precursors) found in petroleum feedstock, they are benign and non-leachable. At elevated temperatures, asphaltenes melt in the form of highly viscous liquid which can be transformed to produce various structured carbon-based products. As noted above, and as known in the art, carbon compounds typically need to be activated in order to adequately function as adsorbents. On the other hand, the asphaltenes described herein can be used in various applications with or without having to be activated. The asphaltene material described herein is particularly effective in water treatment, soil remediation, and agricultural applications.
[0032] In one aspect, the asphaltenes described herein may be used as feedstock for manufacturing carbon-based products in various structures and forms, including but not limited to fiber, mat, and filler. As described herein, the asphaltenes are heated to elevated temperatures and the resulting asphaltene melt can be formed in various shaped carbon materials. The heating temperature can be expected to range from about 150° C. to about 270° C. The preferred heating temperature is about 220° C. In addition to the aspects of the description discussed above, other asphaltene-derived products can be manufactured similar to those carbon-products, as is known in the art.
[0033] In one broad aspect of the present description, a method of using asphaltenes to treat water containing dissolved organics is provided, comprising of mixing the asphaltenes and water for a sufficient time in an adsorption reactor to allow the asphaltenes to adsorb a substantial portion of dissolved organics from the water. It is understood that the asphaltene materials described herein can be used to treat any water source that has a substantial amount of dissolved organics, which includes but is not limited to industrial process water, sewage water, and farm drainage water.
[0034] As discussed above, it is known in the art to use granular activated carbon as an adsorption medium for the treatment of contaminated water, for example. However, as also noted above, the cost of such material makes it prohibitive to use in all applications. On the other hand, although the available surface area of asphaltenes is relatively low in comparison, this material is attractive in view of its relatively low cost and abundancy. Vacuum residua (VR) contain up to about 30 wt % of asphaltenes. The present description therefore offers an economical and environmentally friendly way to treat contaminated water and the like. Also, the present description relies on the utilization of a waste product of the petroleum industry and therefore has environmental benefits.
[0035] In one aspect, the asphaltenes described herein may be used to treat process water from petroleum related operations. The asphaltenes are produced during a solvent deasphalting process, where asphaltenes are produced at high enough quantities such that the concentration of the asphaltenes in the resulting asphaltene/water mixture can be expected to be range from about 10% to about 50% by weight.
[0036] There is provided herein an adsorption reactor that can be, for example, a stirred tank reactor as known in the art, such as a continuous flow stirred tank reactor. In the alternative, the adsorption reactor can be a plug flow reactor, such as a long pipe of sufficient length to provide proper mixing and residence time.
[0037] In one aspect, the asphaltenes described herein may be used for agricultural applications. The present description offers a viable way to decontaminate the soil and remove dissolved organics in farm drainage water.
[0038] In one aspect, the asphaltenes described herein may be mixed with contaminated soils to adsorb contaminants, such as farm chemicals etc., contained therein. In this way, the asphaltenes prevent or at least reduce the contaminants from percolating to the ground water system. The asphaltenes described herein can be laid down as entrenchments, which adsorb chemicals from water discharging into the ground water system.
[0039] In one aspect, the asphaltenes described herein may be as a soil matrix for agricultural purposes. The asphaltenes may also be used as a substitute for a soil matrix for land reclamation purposes.
[0040] As will be understood from the present description, one advantage of using asphaltenes in the presently described manner is that they are a chemically benign natural product. Thus, the unique use of asphaltenes as provided herein serves to mitigate environmental damage by efficiently and cost effectively treating contaminated materials (e.g. water, soil) without causing any deleterious environmental effects.
[0041] Thus, in one aspect, the asphaltenes described herein may be used to decontaminate polluted water streams, such as rivers, channels and other waterways. For example, as illustrated in
[0042] In another aspect, a retainer or other such means may be used to keep the asphaltenes stationary, that is, prevented from being carried away by the flowing water. The retainer material can itself be manufactured using asphaltenes, such as asphaltene fibers as described herein.
[0043] As will be appreciated from the present description and in particular
[0044] In one aspect, the asphaltenes described herein may be used to treat streams and other waterways that are contaminated by animal waste or sewage. In this regard, it is known in the art that animal waste and sewage species (such as feces etc.) can be efficiently and ecologically treated using microorganisms. Such processes are well known. The asphaltenes described herein serve to assist in such biological treatment process by serving as a biofilter medium to which the desired microorganisms are adhered. Such asphaltene biofilter (i.e. asphaltenes combined with microorganisms) may be provided in a bioreactor into which contaminated water and/or soil may added.
[0045] The bioreactor mentioned above can comprise any stirred tank reactor as known in the art, including continuous flow stirred tank reactors and the like. In the alternative, the bioreactor can be a plug flow reactor, such as in the form of a pipe of sufficient length to provide proper mixing and residence time between the contaminated material and the asphaltene biofilter. In another alternative, the bioreactor can be an open tank. In the aforementioned bioreactor systems, the reactor outlets may be packed with asphaltene-derived biofilter media which prevents entrainment and carry-over of microorganisms downstream.
[0046] Further aspects will now be described in additional detail with reference to the following non-limiting examples. It will be understood that these examples are provided solely for the purpose of illustrating aspects of the present description and are not intended to limit the scope thereof.
EXAMPLES
Example 1: Generation of Asphaltenes
[0047] The present description is based on the results from a series of experimental studies that were designed to determine the chemistry and reactivity of asphaltenes in the form of solid granules, which were obtained from the selective asphaltene separation process described in U.S. Pat. No. 7,597,794 (mentioned above) using mined Athabasca oilsands bitumen-derived vacuum residua (VR) as feedstock.
[0048] Tables 1 and 2 show the proximate and elemental analyses of asphaltenes. The data show that the asphaltenes derived from mined oilsands bitumen VR contained high contents of ash, sulfur, and metals, and was selected as a representative sample to illustrate an extreme case scenario of utilization of petroleum asphaltenes. Comparisons of properties of various petroleum derived VR and asphaltenes were reported by Zhao et al. [Zhao, S., Kotlyar, L. S., Woods, J. R., Sparks, B. D., Gao, J., Kung, J., Chung, K. H., Fuel, 2002, 81(6), 737-746] and Zhao et al. [Zhao, S., Kotlyar, L. S., Sparks, B. D., Woods, J. R., Gao, J., Chung, K. H., Fuel, 2001, 80(13), 1907-1914], respectively. The asphaltenes derived from mined oilsands bitumen VR were used as the test sample in the further experiments discussed in the following examples.
TABLE-US-00001 TABLE 1 Proximate analysis of asphaltenes wt % Moisture 0.22 Ash 1.77 Volatile Matter 63.64 Fixed Carbon 34.37
TABLE-US-00002 TABLE 2 Elemental analysis of asphaltenes wt % Carbon 79.2 Hydrogen 8.0 Nitrogen 1.05 Sulfur 6.8 ppm Nickel 339 Vanadium 877 Molybdenum 52.1 Iron 1195 Aluminium 2570 Cobalt 6.35 Magnesium 220 Sodium 323.4 Calcium 537.6 Titanium 446 Manganese 41.3 Cadmium BDL Chromium 7.6 Copper 6.1 Phosphorous 41 Zinc 9.059 Silicon 3660 Lead BDL
Example 2: Assessment of Asphaltene Leaching Capability
[0049] The asphaltenes as described in Example 1 were subjected to a modified leachability test. The asphaltene granules were sieved using a 150-mesh bio-cell filter to yield asphaltene granules with larger than 100-micron particles for the leachability test. A 5-mL glass burette was filled with 100-micron glass beads up to 2-mL gradual level, followed by 0.25 g of 100-micron asphaltene granules. The first test was carried out using de-ionized water. The burette packed with glass beads and asphaltene granules was filled with 5 mL of de-ionized water and was let soaking for 24 hours. After that, the leachate from the burette was drop-wisely discharged and collected. Another 5 mL of fresh de-ionized water was added to the burette. Similar soaking/leaching procedure was repeated three times, resulting in a total of at least 10 mL of leachate collected. The leachate was subjected to inductively coupled plasma mass spectrometry analysis using Shimadzu ICPMS-2030 to determine the concentrations of regulatory elements specified by Environmental Agency (EPA) and other elements [Chung, K. H., Janke, L. C. G., Dureau, R., Furimsky, E., Environmental Sci. & Eng., March 1996, 50-53]. The leachate was also analyzed for polynuclear aromatics using EPA Method 525.1.
[0050] The second test was carried out using pH 4 sulfuric acid solution. Similar control experiments were also carried out in which the burette was filled with glass beads without the asphaltene granules. Table 3 shows the concentrations of regulatory elements specified by EPA's Toxicity Characteristics Leaching Procedure (TCLP) and those of leachates obtained from the leachability tests. The results in Table 3 indicate that the concentrations of all elements in the leachates were much lower than the regulatory levels. Comparing the tests of with and without adding asphaltenes, the concentrations of elements in the leachates were quite similar, indicating that the asphaltenes can be classified as virtually non-leachable. No organic substances were detected in the leachates despite a high sensitivity of the instrument employed.
[0051] The new data derived from the leachability tests indicate that most metal species found in solid asphaltenes are tightly bound to the inner structure of the molecule, and are therefore immobile in solution. These findings are in agreement with surface chemistry analyses reported by Bensebaa et al. [Bensebaa, F., Kotlyar, L., Pleizier, G., Sparks, B., Deslandes, Y., Chung, K., Surf. Interface Anal., 2000, (30) 207-211], where surfaces of asphaltenes from oilsands bitumen were found to be composed of more than 90% carbon, while detectable surface metals were dominated by Al, Si, Mn, and Fe. Also, based on the work of Zhao et al. [Zhao, S., Kotlyar, L. S., Sparks, B. D., Woods, J. R., Gao, J., Chung, K. H., Fuel, 2001, 80(13), 1907-1914], asphaltenes from feedstocks of various sources are expected to behave similar to asphaltenes from oilsands bitumen.
TABLE-US-00003 TABLE 3 Analysis of leachates with and without adding asphaltenes De-ionized water pH 4 sulfuric acid Regulatory Without With Without With level asphaltenes asphaltenes asphaltenes asphaltenes ppb ppb ppb ppb ppb Arsenic 5,000 (0.14) (0.14) (0.14) (0.14) Barium 100,000 15 20 89 91 Cadmium 1,000 (0.037) 0.15 3.7 0.76 Chromium 5,000 (0.081) (0.081) (0.081) (0.081) Lead 5,000 0.037 0.41 22 23 Mercury 200 0.38 0.36 0.56 0.72 Selenium 1,000 (1.7) (1.7) (1.7) (1.7) Aluminium 8.4 6.4 390 1400 Antimony 1.5 1.6 0.71 3.7 Beryllium (0.042) (0.042) 0.057 0.057 Bismuth 0.35 0.25 0.92 0.28 Boron 200 190 440 260 Bromine 3.7 3.9 3.7 5.5 Caesium 0.034 0.039 0.11 0.083 Calcium 85 120 120 85 Cerium 0.012 0.058 3.1 11 Chlorine (11000) (11000) (11000) (11000) Cobolt (0.02) 0.062 0.043 (0.02) Copper (1.4) (1.4) (1.4) (1.4) Dysprosium (0.017) (0.017) 4.4 0.41 Erbium (0.015) (0.015) 0.2 0.67 Europium (0.012) (0.012) 0.18 0.17 Gadolinium (0.014) (0.014) 0.11 0.16 Gallium (0.088) 0.11 0.11 (0.088) Germanium (0.011) (0.011) (0.011) (0.011) Gold (0.006) (0.006) 0.0078 (0.006) Hafnium (0.017) (0.017) 0.03 (0.017) Holmium (0.0042) (0.0042) 0.0092 0.022 Iridium (0.0047) (0.0047) (0.0047) (0.0047) Indium (0.021) (0.021) 0.25 0.14 Iodine 2 1.8 1 1.1 Iron (0.38) (0.38) (0.38) (0.38) Lanthanum (0.012) 0.034 1.8 7.4 Lutetium (0.0091) (0.0091) (0.0091) 0.011 Magnesium 300 450 2300 4500 Manganese (0.14) (0.14) (0.14) (0.14) Neodymium (0.026) (0.026) 0.36 1 Nickel (0.03) 0.32 0.67 (0.03) Niobium 0.093 0.033 (0.0075) (0.0075) Osmium (0.0087) (0.0087) (0.0087) (0.0087) Phosphorus (21) (21) (21) (21) Platinum (0.012) (0.012) (0.012) (0.012) Potassium (11) (11) (11) (11) Praseodymium (0.0069) (0.0069) 0.18 0.42 Rubidium 0.052 (0.04) (0.04) (0.04) Ruthernium (0.015) (0.015) (0.015) (0.015) Samarium (0.024) (0.024) 0.12 0.3 Scandium (0.16) (0.16) (0.16) (0.16) Silicon (880) (880) (880) (880) Sodium 25000 22000 33000 27000 Strontium 4.7 (0.071) (0.071) (0.071) Tantalum (0.0033) (0.0033) (0.0033) (0.0033) Tellurium (0.47) (0.47) (0.47) (0.47) Terbium (0.004) (0.004) 0.15 0.11 Tin 0.28 0.4 0.35 0.33 Titanium (4) (4) (4) (4) Thallium 0.43 0.27 0.51 0.3 Thorium 0.0025 (0.00081) 0.013 0.018 Thulium (0.0034) (0.0034) (0.0034) 0.0083 Tungsten 5.8 1.7 8.5 2.3 Uranium (0.0007) (0.0007) 0.014 0.023 Vanadium (0.04) (0.04) (0.04) (0.04) Ytterbium (0.012) (0.012) 0.045 0.066 Yttrium (0.025) (0.025) (0.025) (0.025) Zinc 0.092 0.54 3.3 0.24 Zirconium 0.034 (0.023) (0.023) (0.023) ( ) Below Detection Limit
Example 3: Use of Asphaltenes for Water Treatment
[0052] In this example, the asphaltenes as discussed above were used as adsorbents for water treatment. The asphaltene granules were sieved using a 150-mesh bio-cell filter to yield asphaltene granules with larger than 100-micron particles for the filtration test. A 5-mL glass burette was filled with 100-micron glass beads up to 2-mL gradual level, followed by 0.25 g of 100-micron asphaltene granules. The test fluids were four drainage water samples obtained from agricultural lands. The burette packed with glass beads and asphaltene granules was filled with 5 mL of drainage water and was let soaking for 24 hours. After that, the filtrate from the burette was drop-wisely discharged and collected. Another 5 mL of drainage water added to the burette. Similar soaking/filtering procedure was repeated five times, resulting in a total of at least 20 mL of filtrate collected. The filtrate was subjected to total organic carbon (TOC) analysis using Shimadzu TOC-L, according to the Chinese standard test method for drinking water quality, GB/T 5749-2006.
[0053] Similar control experiments with various drainage waters were also carried out in which the burette was filled with glass beads without the asphaltene granules. Table 4 shows that TOC's in the drainage water filtrates with and without adding asphaltenes. The results in Table 4 indicate that asphaltenes removed TOC in drainage water. The drainage waters with high TOC contents exhibited high percentages of TOC removal. The test results indicate that asphaltenes are good adsorbent for removing organic carbons in water.
TABLE-US-00004 TABLE 4 Analysis of total organic carbon (TOC) in various farm drainage water and filtrate samples with and without adding asphaltenes Without With asphaltenes asphaltenes Sample TOC, mg/L % Removal 1 32.08 12.75 60.26 2 22.00 12.74 42.09 3 16.45 11.65 29.18 4 10.93 10.45 4.39
[0054] As mentioned above, certain refinery by-products, particularly petroleum coke, have been known to be used for treating water containing dissolved organics. This example therefore illustrates that the use of asphaltenes for water treatment is distinctly advantageous as compared to other materials, such as coke.
Example 4: Suitability of Asphaltenes as a Matrix for Plant Growth
[0055] The asphaltenes as described above were used as soil matrix for planting. Asphaltene granules were blended with a soil sample in various compositions (0, 25, 50, 75, and 100 wt % asphaltenes) and used as planting soils. Garlic was the plant arbitrarily selected for this test. The planting was carried out under ambient environment, as shown in
[0056] After three weeks, the plant growths in various asphaltene-containing soil matrices were determined.
Example 5: Formation of Asphaltene Fibers
[0057] The asphaltenes described above were used as feedstock for producing various fibrous materials. The test was carried out in a single hole laboratory spinneret for melt spinning the asphaltenes which were spun into fine continuous filament, as shown in
[0058] Another test was carried out in a centrifugal melt spinning unit where the asphaltenes were spun into a tangled mat of non-uniform strand fibers, as shown in
[0059] In another test, the centrifugal melt spinning unit was used to produce short asphaltene fibers, as shown in
Example 6: Use of Asphaltene Fibers as a Biofilter
[0060] The asphaltene filler as described in Example 5 was used as biofilter media. An experiment was set up whereby the growth of a culture of Thiobacillus thioparus was monitored in the presence of asphaltene filler with a nutrient solution. Fresh S6 nutrient medium was divided into 90 mL aliquots in 125 mL flasks. Asphaltene filler was added to the flasks to total 1% and 2%. For example, 1 g of the asphaltene filler was added to the solution to represent the 2% sample. A control was also used which contained no asphaltene filler. Finally, the solution was inoculated with 10 mL of a 5-day old culture of Thiobacillus thioparus. Flasks were stored on a shaker at 120 rpm and incubated at 28° C. A small amount of solution was removed after 0, 6, 24, 30, 48, 53 and 168 hours for direct cell count measurements. Each test was carried out in duplicate.
[0061] Thus, this example illustrates that the asphaltenes described herein can be used to retain microorganisms and that such asphaltene-microorganism complex can be used as a biofilter in the treatment of water, soil and or other materials to cause decomposition of contaminants contained therein.
[0062] Although the above description includes reference to certain specific embodiments, various modifications thereof will be apparent to those skilled in the art. Any examples provided herein are included solely for the purpose of illustration and are not intended to be limiting in any way. Any drawings provided herein are solely for the purpose of illustrating various aspects of the description and are not intended to be drawn to scale or to be limiting in any way. The scope of the claims appended hereto should not be limited by the preferred embodiments set forth in the above description, but should be given the broadest interpretation consistent with the present specification as a whole. The disclosures of all prior art recited herein are incorporated herein by reference in their entirety.