MODIFIED CERAMIC MEMBRANES FOR TREATMENT OF OIL SANDS PRODUCED WATER, DISCHARGE WATER AND EFFLUENT STREAMS
20200156012 ยท 2020-05-21
Inventors
Cpc classification
B01D67/00931
PERFORMING OPERATIONS; TRANSPORTING
B01D67/0079
PERFORMING OPERATIONS; TRANSPORTING
B01D69/02
PERFORMING OPERATIONS; TRANSPORTING
B01D67/00791
PERFORMING OPERATIONS; TRANSPORTING
B01D2239/0457
PERFORMING OPERATIONS; TRANSPORTING
B01D71/70
PERFORMING OPERATIONS; TRANSPORTING
C02F2103/365
CHEMISTRY; METALLURGY
B01D69/148
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D69/02
PERFORMING OPERATIONS; TRANSPORTING
B01D61/14
PERFORMING OPERATIONS; TRANSPORTING
B01D67/00
PERFORMING OPERATIONS; TRANSPORTING
B01D69/12
PERFORMING OPERATIONS; TRANSPORTING
B01D71/70
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present invention relates to modified ceramic membranes for the treatment of water. The invention discloses a modified ceramic membrane, comprising: a ceramic membrane, and an outer surface of said ceramic membrane is grafted by a hydrophilic organosilane, wherein said organosilane is selected from the group consisting of: CH30(C2H40)x(CH2)ySi(OCH3)3, where x is >4 and y is >0; CH30(C2H40)x(CH2)ySi(OCH2CH3)3, where x is >4 and y is>0; (CH30)3Si(CH2)yO(C2H40)x(CH2)ySi(OCH3)3, N where x is >4 and y is >0; and (CH3CH20)3Si(CH2)yO(C2H40)x(CH2)ySi(OCH2CI-13)3, where x is >4 and y is >0.
Claims
1. A modified ceramic membrane, comprising: a ceramic membrane, and an outer surface of said ceramic membrane is grafted by a hydrophilic organosilane, wherein said organosilane is selected from the group consisting of: CH.sub.3O(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.3).sub.3; CH.sub.3O(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.2CH.sub.3).sub.3; (CH.sub.3O).sub.3Si(CH.sub.2).sub.yO(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.3).sub.3; and (CH.sub.3CH.sub.2O).sub.3Si(CH.sub.2).sub.yO(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.2CH.sub.3).sub.3, where x is >4 and y is >0.
2. The modified ceramic membrane according to claim 1, wherein a support layer of the ceramic membranes is composed of TiO.sub.2 and/or alumina.
3. The modified ceramic membrane according to claim 1, wherein a selective layer of the membranes is made from alumina.
4. The modified ceramic membrane according to claim 1, wherein a selective layer of the membranes is made from ZrO.sub.2.
5. The modified ceramic membrane according to claim 1, wherein a selective layer of the membranes is made from TiO.sub.2.
6. The modified ceramic membrane according to claim 1, wherein a selective layer of the membranes comprised a mixture of ZrO.sub.2 and TiO.sub.2.
7. The modified ceramic membrane according to claim 1, wherein a selective layer of the membranes comprised a mixture of alumina and TiO.sub.2.
8. The modified ceramic membrane according to claim 1, wherein a selective layer of the membranes comprised a mixture of alumina and ZrO.sub.2.
9. (canceled)
10. The modified ceramic membrane according to claim 1, wherein the hydrophilic organosilane is 2-[methoxy(polyethyleneoxy)6-9 propyl]trimethoxysilane.
11. Use of a modified ceramic membrane for water purification, said modified ceramic membrane comprising: a ceramic membrane, and an outer surface of said ceramic membrane is grafted by a hydrophilic organosilane, wherein said organosilane is selected from the group consisting of: CH.sub.3O(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.3).sub.3; CH.sub.3O(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.2CH.sub.3).sub.3; (CH.sub.3O).sub.3Si(CH.sub.2).sub.yO(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.3).sub.3; and (CH.sub.3CH.sub.2O).sub.3Si(CH.sub.2).sub.yO(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.2CH.sub.3).sub.3, where x is >4 and y is >0.
12. The use of modified ceramic membrane according to claim 11, wherein a support layer of the ceramic membranes is composed of TiO.sub.2 and/or alumina.
13. The use of a modified ceramic membrane according to claim 11, wherein a selective layer of the membranes is made from alumina.
14. The use of a modified ceramic membrane according to claim 11, wherein a selective layer of the membranes is made from ZrO.sub.2.
15. The use of a modified ceramic membrane according to claim 11, wherein a selective layer of the membranes is made from TiO.sub.2.
16. The use of a modified ceramic membrane according to claim 11, wherein a selective layer of the membranes comprised a mixture of ZrO.sub.2 and TiO.sub.2.
17. The use of a modified ceramic membrane according to claim 11, wherein a selective layer of the membranes comprised a mixture of alumina and TiO.sub.2.
18. The use of a modified ceramic membrane according to claim 11, wherein a selective layer of the membranes comprised a mixture of alumina and ZrO.sub.2.
19. The use of modified ceramic membrane according to claim 11, wherein the hydrophilic organosilane is 2-[methoxy(polyethyleneoxy)6-9 propyl]trimethoxysilane.
20. The use of modified ceramic membrane according to claim 11, wherein the water purification is for the treatment of bitumen containing process waters and wastewaters.
21. The use of modified ceramic membrane according to claim 11, wherein the water purification is for the treatment of oily waters and wastewaters in other industry sectors such as coal mining, chemical and steel industries.
22. The use of modified ceramic membrane according to claim 11, wherein the water purification is for treatment of oil sands produced water.
23. The use of modified ceramic membrane according to claim 11, wherein the oil sands produced water is from a steam assisted gravity drainage (SAGD) and Cyclic Steam Stimulation (CSS) process.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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[0043]
[0044]
[0045]
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[0047]
[0048]
DETAILED DESCRIPTION OF THE INVENTION
[0049] The present invention addresses treatment of oil sands produced water, discharge water and effluent streams by using modified ceramic membranes.
[0050] When identifying possible foulants in the filtration of SAGD produced water, bitumen-associated solids must be taken into consideration. These solids include aggregates of quartz, clays and heavy minerals bound together by carbonates, iron oxide and humic matter. However, the most problematic of the bitumen-associated solids have been determined as being ultrafine clays. These ultrafine clays are very thin alumino-silicate clay crystallites onto which organic bitumen molecules and humic matter are adsorbed.
[0051] Therefore, major foulants targeted by the present application are silicates and adsorbed carbon-rich solids. The surfaces of heavy bitumen molecules, such as asphaltenes, have been shown to possess acidic, basic and amphoteric functional groups. This indicates that bituminous fines can exhibit both negative and positive surface charges. Combining this with the fact that the IEPs of the ceramic materials discussed above can vary significantly, it is evident that maintaining the electrostatic repulsion of the identified foulants is a difficult task. Hence, the attraction of these foulants to the ceramic membrane surface is a significant hindrance that needs to be addressed.
[0052] Surfaces of unmodified ceramic membranes are hydrophilic due to the charged hydroxyl groups that populate the top layer. For metal oxide ceramics, the predominant surface charge is dependent on the pH. In other words, if the pH is above the isoelectric point (IEP) of the ceramic material, the predominant surface charge is negative, while at a pH that is below the IEP, the predominant surface charge is positive. The pH is thus an important feed parameter, since it determines the surface charge of the membrane selective layer.
[0053] The present application discloses that charge neutral hydrophilic ceramic membrane surfaces enhance the performance of ceramic membranes in treating produced waters containing bituminous fines.
[0054] According to the present application, organosilane modifying agent was selected to maintain the hydrophilicity of the metal oxide selective layer and reduce the number of hydroxyl groups on the oxide surface. Ceramic membrane disks were modified using this organosilane modifying agent and the modified ceramic membrane were used to treat SAGD produced waters.
[0055] To maintain desirable hydrophilic properties without surface charges, hydrophilic and neutral organosilane was used to modify the surface of ceramic membrane disks.
[0056] The organosilanes used for the silanation of the membrane surfaces is selected from the group consisting of:
[0057] CH.sub.3O(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.3).sub.3, where x is >4 and y is >0;
[0058] CH.sub.3O(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.2CH.sub.3).sub.3, where x is >4 and y is >0;
[0059] (CH.sub.3O).sub.3Si(CH.sub.2).sub.yO(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.3).sub.3, where x is >4 and y is >0; and
[0060] (CH.sub.3CH.sub.2O).sub.3Si(CH.sub.2).sub.yO(C.sub.2H.sub.4O).sub.x(CH.sub.2).sub.ySi(OCH.sub.2CH.sub.3).sub.3, where x is >4 and y is >0.
[0061] The modified ceramic membranes were then used in the filtration of SAGD produced water.
[0062] Modified ceramic membranes have mitigated the irreversible fouling caused by bituminous ultrafines.
[0063] For example, the permeate flux of the 150 and 300 kDa membranes more than doubled after modification in a 20% silane solution.
[0064] Furthermore, the filtered water obtained from the modified membranes was of superior quality, to that of the untreated membrane, as shown by total organic carbon and particle size analysis.
EXAMPLES
[0065] The ceramic membrane disks in the examples are from Sterlitech Corporation (Kent, Wash. USA). The membranes had a diameter of 47 mm, a thickness of 2.5 mm, and offered an overall mass transfer surface area of 13.1 cm.sup.2. The support layer of these membranes was composed of titania. The selective layer of the 0.14 m (1250 kDa) membranes was made from alumina, while the selective layer of the 150 kDa and 300 kDa Molecular Weight Cut-off (MWCO) membranes contained a mix of ZrO.sub.2 and TiO.sub.2.
[0066] Anhydrous ethanol and acetic acid were used in the silane surface grafting process.
[0067] The organosilane used for the silanation of the membrane surfaces is shows in Formula (I) below and listed in Table 1.
##STR00001##
[0068] As shown, a hydrophilic silane containing polyethylene oxide (PEO) chains, [methoxy(polyethyleneoxy)propyl]trimethoxysilane (PEOTMS), was selected as it offered an extremely low water contact angle of 15-16, one of the lowest among commercially available organosilanes.
TABLE-US-00001 TABLE 1 Organosilane used for the silanation of the membrane surfaces Name Formula Notation 2-[METHOXY(POLYETHYLENEOXY)6-9 CH.sub.3O(C.sub.2H.sub.4O).sub.6-9 PEOTMS PROPYL]TRIMETHOXYSILANE (CH.sub.2).sub.3Si(OCH.sub.3).sub.3
[0069] The feed used to conduct the filtration tests was a sample of SAGD produced water was supplied by SAGD operations located in Canada's oil sands in Alberta to CanmetMINING (NRCan).
[0070] To prevent clogging the gear pump used to circulate feed in the test system; the SAGD process water was coarsely filtered using a 50 micron paper filter prior to use.
[0071] Silanating was by deposition from aqueous alcohol solutions. A solution of 95% ethanol/5% water by weight is prepared. The solution is then adjusted to a pH of 4.5-5.5 using acetic acid. Then silanating agent is added with stirring to yield a desired final concentration. The silane concentration was varied from 0.5 to 30 wt %. Following the addition of the silane, 5 minutes were allowed for hydrolysis and silanol formation. The membranes were then immersed into the solution for 2 minutes while being gently agitated. Once removed from the silane solution, the membranes were briefly rinsed in ethanol in order to remove any excess materials and unreacted silane. Finally, the modified membranes were placed in an oven, under nitrogen and at 110 C., for 10 minutes to cure the silane.
[0072] The composition of inorganics in the SAGD produced water samples was determined and is provided in Table 2 below.
TABLE-US-00002 TABLE 2 Average inorganic composition of SAGD produced water feed Com- ponent Na Si B K S Ca Mg Sr Ba Compo- 476 94.1 27.7 15.2 14.2 2.30 0.491 0.159 0.0284 sition (ppm)
[0073] For the experiments conducted, five samples of wastewater feed were extracted from the same drum on different dates. In Table 3, these samples are assigned a label and their pH is given.
TABLE-US-00003 TABLE 3 Label and pH of SAGD wastewater feed samples Feed Sample F1 F2 F3 F4 F5 pH 7.93 8.84 7.58 7.75 7.99
[0074] Both the SAGD wastewater feed and the permeate samples were subjected to a particle size analysis, which allowed for the verification of the molecular weight cut-off of the ceramic membranes. The samples were all analyzed in a Zetasizer Nano S90 (Malvern Instruments Ltd). Samples of 3 mL were placed in the particle size analyzer, and the refractive index of diluted bitumen was taken as 1.58.
[0075] A total organic carbon analysis of all feed and permeate samples was also conducted.
[0076] The filtration experiments were conducted using a cross-flow filtration system. The entire setup was placed in a walk-in fume hood in order to reduce emissions from the SAGD produced water recirculated in the system. All of the filtration tests were conducted at temperatures ranging from 84 to 88 C. The experiments using the 0.14 m membranes were carried out at a transmembrane pressure (TMP) of 68.95 kPa (10 psi), while all other membranes were subjected to a TMP of 172.6 kPa (25 psi). The TMP of each run was maintained constant through the use of a pressure relief valve. In order to remediate fouling, the system was backflushed with permeate for 5 seconds every 295 seconds at 103.4 kPa (15 psi) when using the 0.14 m membrane, and at 206.8 kPa (30 psi) for all other membranes. Initially, 3.7 L of SAGD produced water was loaded into the feed tank and fed to the membrane with a cross-flow velocity of 1.2 m/s. The system was operated with total retentate recycling, while the permeate was collected in a separate container and periodically recycled back to the feed tank. The flowrate of the permeate stream was monitored using a Coriolis flow meter.
[0077] The duration of each run ranged from approximately 3.5 to 4 hours, as this amount of time was considered to be sufficient in order to establish any differences between the modifications.
[0078] The run conditions of the modified membranes using agent PEOTMS and the unmodified membranes are summarized in Tables 4-6 below.
TABLE-US-00004 TABLE 4 Test conditions for the unmodified and modified 150 kDa membrane using agent PEOTMS. Operating pressure 172.6 kPa (25 psi) Trans Membrane Pressure, backflushing with permeate for 5 s every 295 s @ 206.8 kPa (30 psi). Surface SAGD wastewater Feed Temperature Modification Membrane Lot# feed sample ( C.) Unmodified 131113U150 F4 85-87 5% a 131113U150 F4 85-88 10% a 131113U150 F4 85-88 20% a 131113U150 F4 85-88 30% a 131113U150 F5 85-88
TABLE-US-00005 TABLE 5 Test conditions for the unmodified and modified 300 kDa membrane using agent PEOTMS. Operating pressure 172.6 kPa (25 psi) Trans Membrane Pressure, backflushing with permeate for 5 s every 295 s @ 206.8 kPa (30 psi). Surface SAGD wastewater Feed Temperature Modification Membrane Lot # feed sample ( C.) Unmodified 191110U300 F2 87 0.5% a.sup. 191110U300 F2 84-87 1% a 191110U300 F2 85-87 Unmodified 140312U300 F3 86-88 2% a 140312U300 F3 86-87 3% a 140312U300 F2 85-88 15% a 140312U300 F3 86-87 20% a 140312U300 F3 85-87
TABLE-US-00006 TABLE 6 Test conditions for the unmodified and modified 0.14 um membrane using agent PEOTMS. Operating pressure 68.95 kPa (10 psi) Trans Membrane Pressure, backflushing with permeate for 5 s every 295 s @ 103.4 kPa (15 psi). Surface SAGD wastewater Feed Temperature Modification Membrane Lot# feed sample ( C.) Unmodified 190310M014 F1 84-87 2% a 190310M014 F1 87 10% a 190310M014 F2 84-86
[0079] The tables are sectioned according to the manufacturer's membrane lot numbers. The increase or reduction in membrane flux as a result of treatment was compared within a lot and for the same feed. The average flux over the entire filtration period for the 150 kDa, 300 kDa and 0.14 m membranes is shown in
[0080] Referring to
[0081] All membranes modified in a bath containing 20% of PEOTMS or less showed an increase in flux performance compared to the unmodified membranes. The greatest increase in performance was observed for the 150 kDa and 300 kDa membranes at a concentration of 20%, where the flux of the modified membrane was 2.5 and 2.2 times that of the unmodified membrane, respectively.
[0082] The flux of the 0.14 m membrane also showed an increase in flux along the trend of the 150 and 300 kDa membranes. The 30% PEOTMS 150 kDa membrane was run with a different feed sample and was not retained for comparison. Similar cases are seen with the 3% PEOTMS 300 kDa and 10% PEOTMS 0.14 m membranes.
[0083] All membranes were tested from SAGD process water originating from a single drum. However, the pH of the feed varied throughout the tests.
[0084] When membranes of the same batch were run using a feed having a higher pH, a decline in flux was observed. Previous studies have shown that the dissociation of soluble silica, in the form of silicic acid, grows more prominent as the pH surpasses neutral, and silicic acid dissociates into silicate anions, which can then react with the calcium or magnesium found in the wastewater feed to produce insoluble silicates, which may account for the observed decline in permeate flux at higher pH values.
[0085] Nonetheless, the flux of all membranes from the same batch and run with the same feed increased as a result of a treatment with agent PEOTMS. This trend was even observed for silane concentrations as low as 0.5%, as evidenced by the 300 kDa membranes, which demonstrates that the silane modification is effective in releasing bitumen fines from the surface of the modified membrane and thus reducing the severity of the fouling phenomenon.
[0086] The accumulation of colloids and fines on the surface of the membrane is a natural consequence of the filtration process which results in a decline of permeate flux over time. The accumulation of particles is mitigated by the presence of tangential flow over the surface of the membrane and backflushing.
[0087] Particles on the surface of the membrane are partly swept away by feed circulating across the surface of the membrane and released from the surface by backflushing. Over time, the flux will stabilize, where an equal amount of particles are deposited on and released from the surface of the membrane. The number of particles arriving on the surface of the membrane is related to the volume of process water filtered and the concentration of particulates and colloids in the process water.
[0088] During a run, permeate from the membrane was collected in a container placed on the permeate balance. It was recycled periodically back to the feed tank. Initially, the feed tank contained 3.7 L of SAGD produced water. As permeate was collected, the concentration of particulates in the feed increased. It is important to determine the effect of this increase in concentration on membrane flux.
[0089] Hence, membrane flux was plotted as a function of the concentration factor in
[0090]
[0091]
[0092] From
[0093] The total organic carbon (TOC) content of the feed SAGD produced water, as well as the permeate of each run, was measured for use as an indicator of water cleanliness.
[0094] The fraction of the TOC removed in the permeate relative to the feed SAGD wastewater was plotted against both the silane modification concentration in
[0095] In
[0096] In
[0097] Moreover, increasing the concentration of the silane in the modifying solution resulted in further improvement in separation and permeate flux. Hence, for the 150 and 300 kDa membranes, the highest silane concentration tested of 20% was found to be optimal in terms of maximizing flux and separation performance. The results of the TOC analysis demonstrate that the modification is successful in improving the rejection of bituminous organics during filtration of SAGD produced water.
[0098] As a method of characterizing the performance of the ceramic membranes used, the particle size distributions of both the feed and permeate samples were determined. The particle distribution of all feeds was measured.
[0099] The particle size distribution did not vary significantly, containing particles ranging from 220 to 710 nm in diameter. The average of these distributions was plotted in
[0100] The bituminous ultrafines in the tar sands are known to possess dimensions that are inferior to 300 nm, as such the larger particles seen in the produced water feed are attributed to aggregates of bituminous ultrafines that are formed by coagulation. The high salt content in the wastewater may cause the compaction of flat clay platelets to form larger clusters of three-dimensional structures.
[0101] The particle size distribution of the permeates obtained from the 150 kDa, 300 kDa and 0.14 m membranes are shown in
[0102] These distributions are reported along with the corresponding concentration of the silanating agent. All of the distributions show that the particle diameters in the permeates do not exceed 40 nm. The corresponding pore diameters of the 150 kDa and 300 kDa MWCO membranes are approximately 21.5 nm and 30 nm, respectively, based on the size of dextran and pullulan molecules. The distributions observed for permeate samples from these membranes are, therefore, in accordance with their pore sizes. The fact that filtration with the 0.14 m membranes resulted in permeates with similar distributions to those obtained from the 150 and 300 kDa membranes show that the SAGD wastewater feed does not possess a high concentration of particles with a diameter in the approximate range of 40 to 200 nm.
[0103] In the case of the 300 kDa membranes, it was observed that the silane surface modified membranes all gave particle size distributions that were smaller compared to the unmodified membrane. The same can be seen for the 10% PEOTMS 150 kDa and 2% PEOTMS 0.14 m membranes. This is attributable to the pore size reduction that may occur upon surface silanation of the membranes. All other modified membranes resulted in distributions that were similar to, if slightly larger than, the unmodified membranes. Altogether, the small particle sizes observed when analyzing the permeate samples demonstrate that all of the ceramic membranes tested were effective in terms of rejecting the various sub-micron sized particles and colloids found in the feed.
[0104] Ceramic flat ultra- and micro-filtration membrane disks with pore sizes of 150 kDa, 300 kDa and 0.14 m were modified using an organosilane surface modifying agent. The results demonstrate that modified ceramic membranes exhibit fouling-resistant properties to bituminous solids and consequently enhance their performance in treating SAGD produced waters. Modification agent PEOTMS more than doubled the flux of the 150 kDa and 300 kDa ceramic membranes in treating these process waters relative to the unmodified membranes. The modified ceramic membranes were also found to remove up to 72% of the total organic carbon found in SAGD produced water, ensuring water cleanliness for recycling. All of the ceramic membranes tested were shown to reduce the particle sizes in the produced water from >200 nm in the feed to <40 nm in the permeate. The observed trends show that higher silane concentrations in the modification bath lead to higher permeate flux and improved water quality.
[0105] Although the present invention has been described in considerable detail with reference to certain preferred embodiments thereof, other embodiments and modifications are possible. Therefore, the scope of the appended claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.