Method of recovering oil or gas and treating the resulting produced water
10723643 ยท 2020-07-28
Assignee
Inventors
Cpc classification
C02F1/40
CHEMISTRY; METALLURGY
C02F1/40
CHEMISTRY; METALLURGY
C02F2103/365
CHEMISTRY; METALLURGY
C02F9/00
CHEMISTRY; METALLURGY
Y02A20/131
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
C02F1/68
CHEMISTRY; METALLURGY
C02F9/00
CHEMISTRY; METALLURGY
C02F2303/18
CHEMISTRY; METALLURGY
C02F1/68
CHEMISTRY; METALLURGY
C02F1/5245
CHEMISTRY; METALLURGY
E21B43/34
FIXED CONSTRUCTIONS
C02F1/20
CHEMISTRY; METALLURGY
International classification
C02F9/00
CHEMISTRY; METALLURGY
C02F1/40
CHEMISTRY; METALLURGY
C02F1/68
CHEMISTRY; METALLURGY
Abstract
A method or process for treating wastewater containing high organics, silica, boron, hardness, and suspended and dissolved solids. The method includes degasifying the wastewater for the removal of dissolved gases and thereafter chemically softening the wastewater. After the chemical softening step, the wastewater is directed through a media filter or membrane which removes additional solids and precipitants. Thereafter the wastewater is directed through a sodium ion exchange that further softens the wastewater. The effluent from the ion exchange is directed through a cartridge filter and the effluent from the cartridge filter is directed through one or more reverse osmosis units. At a selected phase of the process, prior to the wastewater reaching the reverse osmosis unit or units, the pH of the wastewater is raised and maintained such that the pH of the wastewater reaching a reverse osmosis unit is at a pH greater than 10.5.
Claims
1. A method of recovering oil or gas from an oil or gas well and treating resulting produced water, comprising: a. recovering an oil/water or gas/water mixture from the oil or gas well; b. separating oil from the oil/water mixture or separating gas from the gas/water mixture to produce an oil or gas product and the produced water, and wherein the produced water includes organics, hardness, dissolved solids and suspended solids; c. reducing hardness in the produced water by chemically softening the produced water in a chemical softening unit which results in the formation of hardness precipitants; d. raising the pH of the produced water to 10.5 and above; e. directing the produced water having said pH of 10.5 and above to a mixing tank forming a part of the chemical softening unit and mixing the produced water in said mixing tank and causing crystallization of the precipitants within the produced water; f. after crystallization, removing free oil and crystals from the produced water by directing the produced water through a membrane filter and producing a membrane effluent and a membrane reject stream containing free oil and the crystals; g. recirculating at least a portion of the membrane reject stream to the chemical softening unit and causing the crystals in reject stream to grow larger; h. directing the membrane effluent to an ion exchange unit and further softening the membrane effluent by removing residual calcium and magnesium hardness therefrom and producing an ion exchange effluent and a waste stream; i. after further softening the membrane effluent, directing the ion exchange effluent to at least one reverse osmosis unit and removing dissolved solids from the ion exchange effluent and producing a reject stream and a permeate stream which contain ammonium hydroxide (NH.sub.4OH); j. reducing the concentration of ammonium hydroxide in the reverse osmosis permeate stream by directing the reverse osmosis permeate stream through an ammonia polisher located downstream from the reverse osmosis unit; k. regenerating the ammonia polisher by adding an acid solution to the ammonia polisher which generates a waste stream produced by the ammonia polisher; l. directing at least a portion of the waste stream produced by the ammonia polisher to the chemical softening unit and subjecting the waste stream from the ammonia polisher to treatment in the chemical softening unit; and m. wherein the ammonia polisher produces a treated effluent.
2. The method of claim 1 wherein the produced water includes free oil and wherein the method includes, prior to removing hardness, directing the produced water to a treatment unit disposed upstream of the chemical softening unit for removing free oil and reducing turbidity and the concentration of organics in the produced water and including: mixing an acid and a coagulant with the produced water; after mixing the acid and the coagulant with the produced water, directing the produced water to a gas flotation chamber; mixing a polymer with the produced water in the gas flotation chamber; directing a gas through the produced water in the flotation chamber wherein gas bubbles associated with the gas to facilitate the removal of the free oil and insoluble organic particulates in the produced water as the gas bubbles rise to the top of the produced water in the gas flotation chamber and the method includes skimming the gas bubbles from the produced water; and directing the produced water from the gas flotation chamber and directing at least a portion of the produced water to the chemical softening unit and recycling another portion of the produced water from the gas flotation chamber back to the gas flotation chamber.
3. A method of recovering oil or gas from an oil or gas well and treating resulting produced water, comprising: a. recovering an oil/water or gas/water mixture from the oil or gas well; b. separating oil from the oil/water mixture or separating gas from the gas/water mixture to produce an oil or gas product and the produced water, and wherein the produced water includes organics, silica, hardness, dissolved solids and suspended solids; c. reducing hardness in the produced water by chemically softening the produced water in a chemical softening unit which results in the formation of hardness precipitants; d. raising the pH of the produced water to 10.5 and above; e. directing the produced water having said pH of 10.5 and above to a mixing tank forming a part of the chemical softening unit and mixing the produced water in said mixing tank and causing crystallization of the precipitants within the produced water; f. after crystallization, removing free oil and crystals from the produced water by directing the produced water through a membrane filter and producing a membrane effluent and a membrane reject stream containing free oil and the crystals; g. recirculating at least a portion of the membrane reject stream to the chemical softening unit and causing the crystals in reject stream to grow larger; h. directing the membrane effluent to an ion exchange unit and further softening the membrane effluent by removing residual calcium and magnesium hardness therefrom and producing an ion exchange effluent and a waste stream; i. after further softening the membrane effluent, directing the ion exchange effluent to at least one reverse osmosis unit and removing dissolved solids from the ion exchange effluent and producing a reject stream and a permeate stream which contain organics; j. mixing hydrogen peroxide (H.sub.2O.sub.2) with the permeate stream; k. after mixing hydrogen peroxide with the permeate stream, subjecting the permeate stream to ultraviolet irradiation and converting the hydrogen peroxide in the permeate stream into hydroxyl radicals (HO); l. employing the hydroxyl radicals to oxidize the organic content contained in the permeate stream; and m. after irradiating the permeate stream, mixing sodium bisulfite (NaHSO.sub.3) with the permeate stream to remove residual hydrogen peroxide.
4. The method of claim 3 wherein the produced water includes free oil and wherein the method includes, prior to removing hardness, directing the produced water to a treatment unit disposed upstream of the chemical softening unit for removing free oil and reducing turbidity and the concentration of organics in the produced water and including: mixing an acid and a coagulant with the produced water; after mixing the acid and the coagulant with the produced water, directing the produced water to a gas flotation chamber; mixing a polymer with the produced water in the gas flotation chamber; directing a gas through the produced water in the flotation chamber wherein gas bubbles associated with the gas to facilitate the removal of the free oil and insoluble organic particulates in the produced water as the gas bubbles rise to the top of the produced water in the gas flotation chamber and the method includes skimming the gas bubbles from the produced water; and directing the produced water from the gas flotation chamber and directing at least a portion of the produced water to the chemical softening unit and recycling another portion of the produced water from the gas flotation chamber back to the gas flotation chamber.
5. The method of claim 1 wherein the membrane filter comprises a ceramic membrane and wherein the method includes removing free oil and crystals from the produced water with the ceramic membrane.
6. The method of claim 1 including cooling the ion exchange effluent by directing the ion exchange effluent through a heat exchanger and circulating a cooling medium back and forth between the heat exchanger and a cooling tower.
7. The method of claim 1 further comprising directing the produced water to a gas flotation unit and removing total organic carbon in the produced water prior to chemically softening the produced water; and wherein removing total organic carbon in the produced water includes adding an acid to the produced water such that carbonates and bicarbonates in the produced water are converted into CO.sub.2; adding ferric chloride (FeCl.sub.3) to the produced water to form Fe(OH).sub.3 such that carbon in the produced water is adsorbed onto the Fe(OH).sub.3; adding a polymer to the produced water; and directing gas upwardly through the produced water such that suspended solids in the produced water move upwardly towards the surface of the produced water, removing the suspended solids from the produced water.
8. The method of claim 1 further comprising directing the produced water to a degasification unit removing dissolved gases in the produced water prior to chemically softening the produced water.
9. The method of claim 1 further including mixing an anti-scalant with the produced water upstream of the reverse osmosis unit.
10. The method of claim 3 including cooling the ion exchange effluent by directing the ion exchange effluent through a heat exchanger and circulating a cooling medium back and forth between the heat exchanger and a cooling tower.
11. The method of claim 3 wherein the membrane filter comprises a ceramic membrane and wherein the method includes removing free oil and crystals from the produced water with the ceramic membrane.
12. The method of claim 3 further comprising directing the produced water to a gas flotation unit and removing total organic carbon in the produced water prior to chemically softening the produced water; and wherein removing total organic carbon in the produced water includes adding an acid to the produced water such that carbonates and bicarbonates in the produced water are converted into CO.sub.2; adding ferric chloride (FeCl.sub.3) to the produced water to form Fe(OH).sub.3 such that carbon in the produced water is adsorbed onto the Fe(OH).sub.3; adding a polymer to the produced water; and directing gas upwardly through the produced water such that suspended solids in the produced water move upwardly towards the surface of the produced water, removing the suspended solids from the produced water.
13. The method of claim 3 further comprising directing the produced water to a degasification unit removing dissolved gases in the produced water prior to chemically softening the produced water.
14. The method of claim 3 further including mixing an anti-scalant with the produced water upstream of the reverse osmosis unit.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF THE INVENTION
(8) The present invention relates to a wastewater treatment process for treating wastewater or produced water that typically contains organics, silica, boron, dissolved solids and suspended solids. Various types wastewater may contain these contaminants. For example, in the petroleum industry, produced water typically includes these contaminants. As used herein, the term produced water means water that is produced along with oil or gas in an oil or gas recovery process. Typically, the oil or gas is separated from the water and the separated water is referred to as produced water which is one type of wastewater. The present invention presents a process that can be utilized to treat various types and forms of wastewaters including, but not limited to, produced water and cooling tower blowdown.
(9) As described subsequently herein, the process of the present invention entails chemically softening the wastewater in a process that removes hardness. Thereafter the wastewater is subjected to membrane filtration and ion exchange softening. The wastewater is then directed through one or more reverse osmosis units. To prevent scaling and fouling of the membranes in the reverse osmosis units, an antiscalant is mixed with the wastewater upstream from the reverse osmosis units and the pH of the wastewater is preferably maintained above 10.5. The wastewater can be further treated in an ammonia polisher and an oxidation system. Further, the wastewater can be directed through a heat exchanger so that the temperature of the wastewater is cooled prior to treatment in the reverse osmosis unit(s). Depending on the quality of the wastewater prior to chemical softening, the wastewater may be pretreated in a degasification system or a gas flotation system.
(10) In
(11) Chemical softening unit 20 includes a series of reactors 21, 23, 25 disposed sequentially in relation to one another. Each of the reactors 21, 23, and 25 includes a mixer and inlets 22, 24, and 26 respectively. As discussed in more detail herein, Inlets 22, 24, and 26 are used to inject chemicals such as softening reagents into the water held in reactors 21, 23, and 25. Downstream from the reactors 21, 23, 25 is disposed reactor 27 which includes a vertical tube mixer or crystallization tank. A pump 28 is operative to pump wastewater from reactor 27 to the downstream membrane filter 30.
(12) In one embodiment the membrane filter 30 is a ceramic ultrafiltration membrane and is used to remove suspended solids and precipitants in the water passing through the membrane. Typically, ceramic membranes reject particles having a size of 0.2 m or larger. However, ceramic membranes can be designed such that they reject particle sizes as low as 0.03 m. Subsequently, herein is a general discussion on ceramic membranes and their applicability to treating feed water streams having one or more of the contaminants discussed here. In another embodiment, the membrane filter 30 is a polymeric membrane. Ceramic membranes are desirable when dealing with water having a very high temperature. For example, ceramic membranes are desirable when the water passing therethrough has a temperature approaching 300 F.
(13) As will be appreciated from subsequent portions of this disclosure, a reject recycle line 32 that extends from the membrane filter 30 to the reactor 27. In addition, there is provided a reject waste line 34 that extends from the membrane filter 30 to a filter press 36. Wastewater produced by the filter press 36 is directed through line 38 back to the chemical softening system 20. Membrane filter 30 produces a permeate or effluent that is directed from the membrane filter 30 via line 39 which extends to an ion exchange unit 40. Further, the membrane filter produces a reject stream, a portion of which is recycled via line 32 back to the mixing reactor 27.
(14) Ion exchange unit 40 includes a chemical inlet 41 for regeneration of the ion exchange resin upon exhaustion. A recycle line 44 is operatively connected between the ion exchange unit 40 and the chemical softening unit 20. Ion exchange unit 40 is also operatively connected to a waste line 46 that directs waste produced in the ion exchange unit 40 to disposal. A caustic inlet 45 is disposed downstream from the ion exchange unit 40 and is used to inject a caustic solution into the waste stream produced by the ion exchange unit 40. Ion exchange unit 40 also includes a treated effluent line 43 that extends from the ion exchange unit 40 to a cartridge filter 50. As will be discussed subsequently, the ion exchange unit 40 is utilized to remove residual hardness from the wastewater and, in the case of the embodiment disclosed herein, the ion exchange unit 40 is operated in the sodium mode.
(15) Cartridge filter 50 further filters the water which exits the cartridge filter 50 through filtered water line 52. An antiscalant inlet 47 is disposed upstream of the cartridge filter 50, as shown in
(16) A reject line 61 extends from the reverse osmosis unit 60 and is operatively connected to the waste line 46 which directs waste produced in the reverse osmosis unit 60 to disposal. Treated effluent line 62 extends from the reverse osmosis unit 60 to a discharge area or to a point where the treated water is subjected to additional treatment. A carbon dioxide inlet 63 is disposed downstream from the reverse osmosis unit 60 and is used to inject carbon dioxide into the treated effluent. It is appreciated that the reverse osmosis unit 60 produces a reject stream that is directed into line 61 and a permeate stream that is directed into line 62. In this embodiment and in all subsequent embodiments, the treated effluent can be utilized as a water source for a steam generation device such as a boiler or a once through steam generator. In one example, the treated effluent is used to generate steam which is injected into an oil and/or gas bearing formation in order to extract oil and/or gas therefrom.
(17) As stated above, the wastewater treatment system 10 of the present invention can be used to treat various types and forms of influent wastewater streams such as a produced water stream or a cooling tower blowdown stream.
(18) While
(19) With reference to
(20) Second reverse osmosis unit 70 produces a permeate stream and a reject stream. The reject stream is directed into line 72 and recycled to a point upstream of the first reverse osmosis unit 60. The permeate produced by the second reverse osmosis unit 70 is directed into line 74. In this embodiment, a carbon dioxide inlet 63 is disposed downstream of the reverse osmosis unit 70 and is used to inject carbon dioxide into the permeate passing through line 74.
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(24) In the process depicted in
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(27) With reference to the specific processes illustrated in the figures, feed water or wastewater influent is directed to the chemical softening unit 20. The purpose of the chemical softening process is to reduce total hardness in the feed water to solubility limits, typically less than approximately 55 mg/l as CaCO.sub.3. Further, the softening process carried out in the chemical softening unit 20 removes at least a portion of the silica from the feed water.
(28) As shown in the figures, a first alkali based reactant is added to the wastewater in reactor 21 through inlet 22. In one embodiment the first alkali based reactant is calcium hydroxide (Ca(OH).sub.2). As Ca(OH).sub.2 is mixed with the wastewater, carbon dioxide (CO.sub.2), calcium bicarbonate (Ca(HCO.sub.3).sub.2, and magnesium bicarbonate (Mg(HCO.sub.3).sub.2 dispersed throughout the wastewater react with the Ca(OH).sub.2 to precipitate some calcium carbonate (CaCO.sub.3) and some magnesium hydroxide (Mg(OH).sub.2). Ca(OH).sub.2 also reacts with magnesium sulfate (MgSO.sub.4) and magnesium chloride (MgCl.sub.2) in the wastewater to precipitate magnesium hydroxide (Mg(OH).sub.2).
(29) In one embodiment, magnesium oxide (MgO) is also added to the wastewater. MgO can be added to the water prior to the water entering reactor 21 or MgO can be added to the water while in reactor 21. As MgO is mixed with the water, it is converted into magnesium hydroxide (Mg(OH).sub.2) which acts as an adsorbent. Mg(OH).sub.2 in the water, created through the addition of Ca(OH).sub.2 and/or MgO, adsorbs silica dispersed throughout the water.
(30) Wastewater is transferred from reactor 21 to reactor 23 where a second alkali based reactant is added to the water through inlet 24. In one embodiment, the second alkali based reactant is sodium carbonate (Na.sub.2CO.sub.3). As Na.sub.2CO.sub.3 is mixed with the water, the Na.sub.2CO.sub.3 reacts with calcium sulfate (CaSO.sub.4) and calcium chloride (CaCl.sub.2) in the water to precipitate CaCO.sub.3.
(31) The addition of these reagents, for example Ca(OH).sub.2, MgO, and Na.sub.2CO.sub.3, causes hardness compounds to precipitate from the wastewater stream being treated. After precipitation, these precipitants can be removed by filtration such as with the filtration membrane and cartridge filter.
(32) After the wastewater is treated in the reactor 23, the wastewater is directed to reactor 25 where a third alkali based reactant can be added to the water through inlet 26. In one embodiment, the third alkali based reactant is a caustic solution, such as sodium hydroxide (NaOH). The third alkali based reactant raises the pH of the water to above 10.5. As discussed in more detail below, it is often preferable to maintain the pH of the water in the range of 10.5 to 11.5.
(33) The above description includes the addition of several alkaline reagents and a caustic reagent. However, it is noted that the addition of each of the above reagents is merely an exemplary embodiment of the present invention. Further, the present invention encompasses embodiments in which only one or two alkaline reagents and a caustic reagent are added to the water. For example, it may be effective to add only one alkaline reagent and one caustic reagent to the water to remove hardness from the water and effectively increase the pH of the water.
(34) After the water has been treated in reactor 23, the water is directed to the mixing reactor 27 where the wastewater is vigorous mixed in the vertical mixer. Mixing in the mixing reactor 27 causes precipitants to grow larger which makes it easier for the downstream membrane filter 30 to reject the precipitants. As discussed below, the reject stream of the membrane filter 30 is recycled via line 32 to the mixing reactor 27. The mixing action of the vertical tube mixer in reactor 27, coupled with the recycle of solids or precipitants from the membrane filter 30, gives rise to a crystallization process where the solids form crystals and the mixing action realized in the reactor 27 causes the crystals to grow larger. Note, that in mixing reactor 27, the vertical tube mixer includes a tube-like structure disposed in the reactor and one or more mixers disposed within the two structures. In mixing the various reagents and precipitants, wastewater in reactor 27 is induced into the top of the tube and caused to move downwardly through the tube and out the bottom of the tube. This continuous mixing action causes the wastewater, along with the precipitants or crystals to move back up toward the top of the reactor outside of the tube. Thereafter the wastewater re-enters the top of the tube. Thus, this continuous mixing action causes the wastewater to be drawn down through the tube, out of the tube, and up the sides of the reactor and back down through the tube. This type of mixing action promotes an efficient crystallization process where the precipitants tend to grow larger. After the crystals or precipitants have increased in size, the effluent from the mixing reactor 27 is directed to membrane filter 30 via the pump 28. Typically, the effluent from the mixing reactor 27 is directed through the membrane filter 30 at a pressure of approximately 30 psi to approximately 60 psi.
(35) Membrane filter 30 removes suspended solids and particulates. The present wastewater treatment system and process is effective in treating produced water which typically includes free oil and even emulsified oil. See
(36) Membrane filter 30 also produces a filtrate which is directed to the ion exchange unit 40 through filtrate line 39. As the filtrate passes through the ion exchange unit 40, Ca.sup.2+ and Mg.sup.2+ in the filtrate are removed through a cation exchange process. For example, in one embodiment, the ion exchange unit 40 includes a Na.sup.+ based cation resin. The Ca.sup.2+ and Mg.sup.2+ in the filtrate are exchanged with the Na.sup.+ in the resin. Moreover, other metal cations present in the filtrate are exchanged with the Na.sup.+ in the resin. Thus, the ion exchange unit 40 further reduces the total hardness of the wastewater and reduces the concentration of other soluble metals in the water.
(37) As the resin in the ion exchange unit 40 becomes saturated with Ca.sup.2+ and Mg.sup.2+, and other metal ions, the resin needs to be regenerated to maintain its effectiveness. To regenerate the resin, an acid solution added to the ion exchange unit 40 through inlet 41 is directed through the resin. A portion of the waste produced through the resin regeneration is recycled to the chemical softening unit 20 through recycle waste line 44. A caustic solution is added to the waste stream in the waste line 44 through inlet 45. This addition reduces the pH of the acidic waste stream. Another portion of the waste stream produced through resin regeneration is directed to the waste line 46 and sent for disposal.
(38) The softened effluent from the ion exchange unit 40 is directed from the ion exchange unit 40 through line 43 to the cartridge filter 50 which removes fine particulates present in the effluent. An antiscalant is added to the effluent through inlet 47 upstream of the cartridge filter 50 to maintain a soluble chemical equilibrium for the scale forming compounds across the downstream reverse osmosis unit(s) 60, 70. In processes such as described herein, it is difficult to eliminate scaling or fouling of the membranes associated with the reverse osmosis unit(s) by chemical softening and softening in the ion exchange unit 40. For that reason, the antiscalant is added to the feed water or wastewater stream ahead of a first reverse osmosis unit 60. In another embodiment, the antiscalant inlet 47 can also be disposed downstream from the cartridge filter 50 and upstream from the reverse osmosis unit 60. The filtered water exits the cartridge filter 50 through filtered water line 52 and is directed to a first reverse osmosis unit 60 via a pump 54. To ensure that the downstream reverse osmosis units do not experience extensive fouling or scaling, in one embodiment it is desirable that the filtered water from the cartridge filter 50 have a total hardness of less than 0.20 mg/l CaCO.sub.3, a free oil concentration of less than 0.50 mg/l, and a silt density index of less than 4.0.
(39) The first reverse osmosis unit 60 reduces organics, silica, boron, and total dissolved solids present in the water. Accordingly, the first reverse osmosis unit 60 produces a reject stream having a relatively high concentration of contaminants and a treated effluent stream having a relatively low concentration of contaminants. The reject stream is directed through reject line 61 to waste line 46 for disposal. The treated effluent or permeate is directed through the treated effluent line 62 to a discharge area or to a point where the treated effluent is subjected to additional treatment. In one embodiment, it is desirable for the treated effluent or permeate for the first reverse osmosis unit 60 to have less than 1,000 S/cm conductivity. Carbon dioxide (CO.sub.2) is injected into the treated effluent in the treated effluent line 62 through inlet 63. The addition of CO.sub.2 decreases the pH of the wastewater. As discussed above, the treated effluent from the reverse osmosis unit 60 has a generally high pH. When CO.sub.2 is added to the water it dissolves and forms a carbonic acid, H.sub.2CO.sub.3, a generally weak acid. Thus, the addition of CO.sub.2 is beneficial when the treated effluent is discharged or subjected to downstream treatment and requires a downward adjustment in pH.
(40) Appearing below under Table 1 is a summary of exemplary data for a cooling tower blowdown feed water treated in the process described above. Note that calcium hardness is reduced in the chemical softening unit 20 from 500 ppm to 8 ppm. In addition, magnesium hardness is reduced in the chemical softening unit from 100 ppm to 2 ppm. Further, silica is reduced in the chemical softening unit from 150 ppm to 80 ppm. Again, the pH in the chemical softening process is raised to 10.7. The table below refers to free oil, emulsified oil, and soluble oil. As used herein, if an oil particle is 30 m or greater, it is referred to as free oil. If the oil particle is between 1 and 30 m, it is referred to as emulsified oil. If the oil particle is less than 1 m, it is referred to as soluble oil.
(41) It is noted that the chemical softening unit 20 does not decrease the total alkalinity in the feed water. Rather, the chemical softening unit actually increases the alkalinity in the feed water. For example, in preliminary tests and as described below, the feed water had a total alkalinity of 150 ppm as CaCO.sub.3. After treatment in the chemical softening unit, the effluent had a total alkalinity of 400 ppm as CaCO.sub.3. A decrease in total alkalinity only occurs after treatment in the RO system. Maintaining a high alkalinity in the water increases the rejection rate of organics in the water passing through the RO system.
(42) TABLE-US-00001 TABLE 1 Cooling Tower Chemical Ceramic Ion Blowdown Softening Membrane Exchange RO System Treated Feed Water Effluent Filtrate Effluent Permeate Effluent pH (S.U.) 6.5-8.5 10.7 10.7 10.7 10.2 7.5 Total Alkalinity 150 400 400 400 <75 <75 (ppm as CaCO.sub.3) Ca-Hardness 500 8.0 8.0 0.08 Non-detect Non-detect (ppm as CaCO.sub.3) Mg-Hardness 100 2.0 2.0 0.02 Non-detect Non-detect (ppm as CaCO.sub.3) Dissolved Silica 150 80 80 80 <0.5 <0.5 (ppm) Free Oil (ppm) 10.0 10.0 <0.2 <0.2 Non-detect Non-detect Emulsified Oil 5.0 5.0 <0.2 <0.2 Non-detect Non-detect (ppm) Soluble Oil (ppm) 10.0 10.0 10.0 10.0 <0.5 <0.5 TSS (ppm) 30 1,000 <0.2 <0.2 Non-detect Non-detect TDS (ppm) 4,000 4,500 4,500 4,500 150 150 Boron (ppm) 5.0 5.0 5.0 5.0 <0.5 <0.5 Total Organic 30 30 30 30 <0.5 <0.5 Carbon (ppm)
(43) In another embodiment, shown in
(44) Second reverse osmosis unit 70 also produces a reject stream having a relatively high concentration of contaminants and a permeate or treated effluent stream having a relatively low concentration of contaminants. The reject stream is directed through recyclable waste line 72 to the first reverse osmosis unit 60. CO.sub.2 is injected into the treated effluent through inlet 76 disposed downstream from the second reverse osmosis unit 70. As mentioned above, the addition of CO.sub.2 decreases the pH of the water and thus is beneficial if the treated effluent is being discharged or subjected to downstream treatment which requires a downward adjustment in pH.
(45) The present process aims to control the pH of the wastewater passing through the one or more reverse osmosis units 60, 70 above 10.5. Maintaining a high pH of the water substantially reduces organic fouling and silica scaling of the membranes in the reverse osmosis units. Further, the solubility of organics generally increases with pH. For example, at a pH over 10 the solubility of organics is approximately 350 mg/l. However, at a pH of 6 the solubility of organics is just above 50 mg/l. The same relationship holds true for the solubility of silica. For example, the solubility of silica at a pH of about 10.5 is almost 900 mg/l. However, at a pH of 8 the solubility of silica is about 100 mg/l. By maintaining the pH of the feed water above 10.5, these particular scaling and fouling contaminants are maintained in solution and can be rejected by the one or more reverse osmosis units 60 or 70 without scaling or fouling.
(46) The process described above can also be modified to include other processes. For example, as shown in
(47) As the resin in the ammonia polisher 80 becomes saturated with NH.sub.4.sup.+, the resin needs to be regenerated to maintain its effectiveness. To regenerate the resin, an acid solution is added to the ion exchange unit 40 through inlet 82. A portion waste produced through resin regeneration is recycled to the chemical softening unit 20 through recyclable waste line 88. Another portion of the waste stream produced through the resin regeneration is directed to the waste line 46 and sent for disposal. After the water is treated in the ammonia polisher 80, a caustic solution is added to the treated water in the treated water line 84 through inlet 89 disposed downstream from the ammonia polisher 80. The addition of the caustic solution is preferred if the treated water exiting the ammonia polisher 80 has a generally low pH. Typically, caustic solution is added to the treated water to increase the pH of the treated water to between approximately 6.5 and approximately 9 in order to meet environmental regulations. Then, the treated water in treated water line 84 is directed toward a discharge area or to a point where the treated water is subjected to additional treatment.
(48) In the embodiment shown in
(49) The irradiated water exits the ultraviolet light unit 92 through line 93 and is then injected with a NaHSO.sub.4 solution through inlet 94. The NaHSO.sub.4 solution removes residual H.sub.2O.sub.2 from the water. The irradiated water can also be injected with a caustic solution through inlet 95. The addition of a caustic solution is preferred if the irradiated water has a generally low pH. As described above, the caustic solution is added to the water to increase the pH of the water to between approximately 6.5 and approximately 9 in order to meet environmental regulations. Then, the irradiated water in line 93 is either directed toward a discharge area or to a point where the treated water is subjected to additional treatment.
(50) In another embodiment, shown in
(51) Further, after the treated effluent is treated in the first and second reverse osmosis units 60, 70, a portion of the treated water from the second reverse osmosis unit 70 is directed to the cooling tower 102 through line 108. This water is used as make-up cooling water for use in the heat exchanger 100.
(52) Appearing below under Tables 2 and 3 is a summary of exemplary data for oil field produced water treated in the process described above. Note that calcium hardness (expressed as CaCO.sub.3) was reduced in the chemical softening unit 20 from 400 ppm to 8 ppm. In addition, magnesium hardness (expressed as CaCO.sub.3) was reduced in the chemical softening unit from 100 ppm to 2 ppm. Further, silica was reduced in the chemical softening unit from 300 ppm to 80 ppm. The pH in the chemical softening process was raised to 10.7. Again, it is noted that the chemical softening unit does not decrease the total alkalinity in the feed water. Rather, the chemical softening unit actually increases the alkalinity in the feed water. For example, in the preliminary test described below, the feed water had a total alkalinity of 300 ppm as CaCO.sub.3. After treatment in the chemical softening unit, the effluent had a total alkalinity of 400 ppm as CaCO.sub.3. A decrease in total alkalinity only occurs after treatment in the RO system. Maintaining a high alkalinity in the water increases the rejection rate of organics in the water passing through the RO system.
(53) TABLE-US-00002 TABLE 2 Oil Field Chemical Ceramic Ion Produced Softening Membrane Exchange Water Effluent Filtrate Effluent pH (S.U.) 6.5-8.5 10.7 10.7 10.7 Total Alkalinity (ppm as 300 400 400 400 CaCO.sub.3) Ca-Hardness (ppm as 400 8.0 8.0 0.08 CaCO.sub.3) Mg-Hardness (ppm as 100 2.0 2.0 0.02 CaCO.sub.3) Dissolved Silica (ppm) 300 80 80 80 Free Oil (ppm) 100.0 100.0 <0.2 <0.2 Emulsified Oil (ppm) 10.0 10.0 <0.2 <0.2 Soluble Oil (ppm) 100.0 100.0 100.0 100.0 TSS (ppm) 50 1,000 <0.2 <0.2 TDS (ppm) 7,000 7,500 7,500 7,500 Boron (ppm) 26.0 26.0 26.0 26.0 Total Organic Carbon 100 100 100 100 (ppm) Total Ammonia (ppm) 20.0 20.0 20.0 20.0
(54) TABLE-US-00003 TABLE 3 Ammonia Advanced RO System Polisher Oxidation Treated Permeate Effluent Effluent Effluent pH (S.U.) 10.2 4.5 6.5 7.5 Total Alkalinity (ppm as <75 Non- 20 20 CaCO.sub.3) detect Ca-Hardness (ppm as Non- Non- Non- Non- CaCO.sub.3) detect detect detect detect Mg-Hardness (ppm as Non- Non- Non- Non- CaCO.sub.3) detect detect detect detect Dissolved Silica (ppm) <0.5 <0.5 <0.5 <0.5 Free Oil (ppm) Non- Non- Non- Non- detect detect detect detect Emulsified Oil (ppm) Non- Non- Non- Non- detect detect detect detect Soluble Oil (ppm) <0.5 <0.5 <0.5 <0.5 TSS (ppm) Non- Non- Non- Non- detect detect detect detect TDS (ppm) 150 <10 <20 <20 Boron (ppm) <0.5 <0.5 <0.5 <0.5 Total Organic Carbon <0.5 <0.5 Non- Non- (ppm) detect detect Total Ammonia (ppm) 20.0 <0.1 <0.1 <0.1
(55) Other embodiments of the present invention include pretreatments of the feed water prior to treatment in the chemical softening unit 20. For example, in
(56) The present invention may also include a pretreatment gas flotation system 120. For example, in
(57) It is further noted that the present invention is not limited to the specific combination of elements described above or shown in the drawings. Rather, the present invention encompasses embodiments that do not include all of the above elements. For example, the embodiments shown in
(58) However, each of the embodiments in the present invention includes a membrane filtration unit. As described above, the membrane filtration unit can comprise a ceramic membrane. Specific details of ceramic membranes are not dealt with herein because the details of such membranes not per se material to the present invention, and further, ceramic membranes are known in the art. For a review of general ceramic membrane technology, one is referred to the disclosures found in U.S. Pat. Nos. 6,165,553 and 5,611,931, the contents of which are expressly incorporated herein by reference. These ceramic membranes, useful in the processes disclosed herein, can be of various types. In some cases the ceramic membrane may be of the type that produces both a permeate stream and a reject stream. On the other hand, the ceramic membranes may be of the dead end type, which only produces a permeate stream and from time-to-time the retentate is backflushed or otherwise removed from the membrane. For example, when treating produced water, the ceramic membrane may require cleaning by back pulsing the permeate through the membrane. However, when the transmembrane pressure across the ceramic membrane reaches a substantially high pressure, such as between approximately 40 psi and 45 psi, it may be desirable to perform a clean-in-place of the ceramic membrane.
(59) The structure and materials of the ceramic membranes as well as the flow characteristics of ceramic membranes varies. When ceramic membranes are used to purify produced water, the ceramic membranes are designed to withstand relatively high temperatures as it is not uncommon for the produced water being filtered by the ceramic membranes to have a temperature of approximately 90 C. or higher.
(60) Ceramic membranes normally have an asymmetrical structure composed of at least two, mostly three, different porosity levels. Indeed, before applying the active, microporous top layer, an intermediate layer with a pore size between that of the support, and a microfiltration separation layer. The macroporous support ensures the mechanical resistance of the filter.
(61) Ceramic membranes are often formed into an asymmetric, multi-channel element. These elements are grouped together in housings, either a single element in a housing or multiple elements in a housing, and these membrane modules can withstand high temperatures, extreme acidity or alkalinity and high operating pressures, making them suitable for many applications where polymeric cannot be used. Several membrane pore sizes are available to suit specific filtration needs covering the microfiltration, the ultrafiltration, and nanofiltration ranges from 1 micron down to 250 Dalton MWCO).
(62) Ceramic membranes today run the gamut of materials (from alpha alumina tosilicon carbide). The most common membranes are made of Al, Si, Ti or Zr oxides, with Ti and Zr oxides being more stable than Al or Si oxides. In some less frequent cases, Sn or Hf are used as base elements. Each oxide has a different surface charge in solution. Other membranes can be composed of mixed oxides of two of the previous elements, or are established by some additional compounds present in minor concentration. Non-oxide membranes are also available such as silicon nitride or silicon carbide with silicon carbide membranes being most prevalent. Low fouling polymeric coatings for ceramic membranes are also available.
(63) Ceramic membranes are typically operated in the cross flow filtration mode. This mode has the benefit of maintaining a high filtration rate for membrane filters compared with the direct flow filtration mode of conventional filters. Cross flow filtration is a continuous process in which the feed stream flows parallel (tangential) to the membrane filtration surface and generates two outgoing streams.
(64) A small fraction of feed called permeate or filtrate, separates out as purified liquid passing through the membrane. The remaining fraction of feed, called retentate or concentrate contains materials rejected by the membrane.
(65) The separation is driven by the pressure difference across the membrane, or the trans-membrane pressure. The parallel flow of the feed stream, combined with the boundary layer turbulence created by the cross flow velocity, continually sweeps away particles and other material that would otherwise build up on the membrane surface.
(66) The process of the present invention has many applications. The process can be used in oil field produced water treatment for surface discharge or for use in steam generating devices to generate steam for use in oil recovery. Likewise, the process can be used in gas field produced water treatment for surface discharge. In addition, the process of the present invention can be used to treat refinery wastewater for reuse with zero liquid discharge. Moreover, the process or the present invention has applications for treating cooling tower blowdown as well as FGD scrubber blowdown. Still further, the process of the present invention has applications in treating industrial wastewater, such as automotive wastewater.