WO2008073963A1 - Method for treating wastewater or produced water - Google Patents
Method for treating wastewater or produced water Download PDFInfo
- Publication number
- WO2008073963A1 WO2008073963A1 PCT/US2007/087206 US2007087206W WO2008073963A1 WO 2008073963 A1 WO2008073963 A1 WO 2008073963A1 US 2007087206 W US2007087206 W US 2007087206W WO 2008073963 A1 WO2008073963 A1 WO 2008073963A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wastewater
- produced water
- softening
- directing
- ion exchange
- Prior art date
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 134
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000007787 solid Substances 0.000 claims abstract description 50
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 46
- 238000005342 ion exchange Methods 0.000 claims abstract description 37
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 29
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract 3
- 239000010802 sludge Substances 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 27
- 239000002699 waste material Substances 0.000 claims description 24
- 239000000701 coagulant Substances 0.000 claims description 21
- 239000003518 caustics Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000000356 contaminant Substances 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 12
- 239000004571 lime Substances 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000000280 densification Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 17
- 238000004064 recycling Methods 0.000 claims 5
- 230000000368 destabilizing effect Effects 0.000 claims 3
- -1 organics Substances 0.000 claims 3
- 230000003472 neutralizing effect Effects 0.000 claims 2
- 235000010216 calcium carbonate Nutrition 0.000 claims 1
- 230000003750 conditioning effect Effects 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 8
- 238000007872 degassing Methods 0.000 description 8
- 238000004065 wastewater treatment Methods 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010847 non-recyclable waste Substances 0.000 description 2
- 239000010819 recyclable waste Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
- B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2317/00—Membrane module arrangements within a plant or an apparatus
- B01D2317/02—Elements in series
- B01D2317/025—Permeate series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
- C02F5/06—Softening water by precipitation of the hardness using calcium compounds
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- Ion exchange processes and reverse osmosis processes have been used for desalting produced water or wastewater.
- Current practices involving the operation of reverse osmosis systems usually maintain a neutral pH condition, which is a pH of approximately 6-8.
- the recovery across reverse osmosis systems is often limited by scaling due to silica or fouling due to organics. That is, high concentrations of silica in the feed water tend to scale the reverse osmosis membranes due to the concentration of silica exceeding solubility limits. Organics that exceed solubility limits also tend to foul the reverse osmosis membranes.
- the present invention entails a method or process for treating produced water or wastewater utilizing reverse osmosis units to remove hardness, silica, dissolved and suspended solids and boron, and which maintains the pH of the produced water or wastewater entering the reverse osmosis unit to above 10.5.
- the present invention entails directing feed water (wastewater or produced water) through a chemical softening process that reduces hardness, reduces the concentration of silica and soluble metals, and removes at least some of the suspended solids.
- feed water wastewater or produced water
- one or more alkaline reagents are added to the feed water for the purpose of raising the pH to above 10.5.
- a further object of the present invention is to provide a system for treating wastewater that includes a chemical softening unit or subsystem having a series of reactors and a clarifier.
- a series of injection lines for injection a coagulant, one or more alkaline reagents, and a polymer.
- Disposed downstream from the reactors and the clarifier are one or more filtration units and one or more ion exchange units for further filtering the feed water and further reducing the hardness of the feed water.
- Figure 1 is a schematic illustration of the process of the present invention
- Figure 1A illustrates the use of a vertical tube mixer in the process of the present invention.
- FIG. 2 is a schematic illustration of the wastewater treatment process shown in Figure 1 , but illustrating a number of optional processes.
- Figure 3 is a graph showing the relationship between solubility of organics and pH.
- Figure 4 is a graph showing the relationship between the solubility of silica and pH. DESCRIPTION OF THE INVENTION
- the present invention relates to a wastewater treatment process for treating wastewater or producing water that contains organics, silica, boron, dissolved solids and suspended solids.
- Various types and forms of wastewater may contain these contaminants.
- produced water discharged from oil recovery operations typically includes these contaminants. Treatment of such produced water to meet government discharge regulations is challenging.
- the term "wastewater” broadly means an aqueous stream that includes contaminants to be renewed by treatment, and includes, for example, produced water, surface water and well water.
- the process of the present invention entails chemically softening and clarifying the wastewater in a process that removes hardness, and through a clarifier, removing suspended solids and precipitants.
- the treated and conditioned wastewater is directed through one or more reverse osmosis units.
- the pH of the wastewater is controlled and maintained above 10.5.
- the wastewater treatment system of the present invention is shown therein and indicated generally by the numeral 10.
- the system includes a chemical softening unit 30, a multimedia filtration unit 40, an ion exchange filtration unit 50, a cartridge filtration unit 60, and at least one single pass reverse osmosis unit 70.
- a part of the chemical softening unit 30 is a series of reactors 31 , 32, 33 and 34, and a clarifier 35.
- Each of the reactors 31 , 32, 33 and 34 include a mixer.
- Clarifier 35 disposed downstream from the reactors 31 , 32, 33 and 34 is of a conventional design, and in the embodiment illustrated herein, includes a settling tank with lamella or separating plates and a bottom scraper.
- a return sludge line 36 extends from the clarifier 35 to the first reactor 31 or second reactor 32.
- a waste sludge line 37 also extends from the clarifier 35.
- Extending between the clarifier 35 and the multimedia filter 40 is a connecting line 41.
- Clarified effluent from the clarifier 35 is directed through line 41 to the multimedia filter 40.
- a coagulant injection site can be provided in line 41.
- Various types of media filters can be utilized.
- a membrane filtration unit which could be ultra filtration or micro filtration, could be used.
- the multimedia filter 40 would be utilized which would employ layers of anthracite, sand and garnet to remove suspended solids and precipitants in the wastewater passing through the filter.
- a waste stream will be produced by the multimedia filter 40 and this waste stream will be recycled through return line 42 to be mixed with the influent feed water that is directed through line 11 into the chemical softening unit 30.
- a waste line 43 that discharges at least some of the waste stream or sludge expelled form the multimedia filter 40.
- Extending from the multimedia filter 40 to the ion exchange unit 50 is a connecting line 45. Purified effluent leaving the multimedia filter 40 is directed through line 45 to the ion exchange unit 50.
- Ion exchange unit 50 includes a chemical inlet line 46 for regeneration of the Ion Exchange Resin upon exhaustion and a return recyclable waste line 47. The recyclable portion of the regeneration waste is recycled to the chemical softening unit. There will be non-recyclable waste leaving the Ion Exchange softener via line 48.
- ion exchange unit 50 Connected between the ion exchange unit 50 and the cartridge filter 60 is another connecting line 49. Treated or purified effluent from the ion exchange unit 50 is directed through line 49 to the cartridge filter 60. Cartridge filter 60 further filters the wastewater and produces a waste or contaminant stream that is discharged through line 51. An antiscalant or dispersant is added ahead of the cartridge filter 60 to provide a soluble chemical equilibrium for the scale forming compounds across the reverse osmosis unit 20.
- a connecting line 52 Connected between cartridge filter 60 and the reverse osmosis unit 70 is a connecting line 52. Treated or purified effluent from the cartridge filter 60 is directed through line 52 to the reverse osmosis unit 70.
- Reverse osmosis unit 70 produces a treated effluent or product water that is directed from reverse osmosis unit 70 through line 72 to a discharge area or to a point where the treated wastewater is subjected to additional treatment.
- a reject line 71 Leading from the reverse osmosis unit 70 is a reject line 71 that discharges a reject stream produced by the reverse osmosis unit 70.
- a feed water or wastewater influent is directed through line 11 to the chemical softening unit 30.
- a coagulant is mixed with the feed water in reactor 31.
- the coagulant acts to destabilize the solids generated during the softening process and further facilitates or enhances the separation of solids from the liquid in subsequent portions of the process.
- Various coagulants can be used. Typical coagulants which are utilized are ferric chloride, aluminum sulfate, polyaluminum chloride, and ferrous or ferric sulfate. Dosage may vary depending on the nature and characteristics of the feed water, but in many cases, the dosage will vary in the range of 10-50 mg/l.
- the feed water is directed down stream to reactors 32 and 33.
- lime is added to the feed water in reactor 32 and caustic is added to the feed water in reactor 33. Both the lime and caustic are mixed with the feed water.
- Lime converts carbon dioxide to bicarbonate ions and also neutralizes the bicarbonate alkalinity of the feed water and removes calcium carbonate hardness.
- the caustic removes magnesium hardness present in the feed water and raises the pH of the feed water.
- the pH of the feed water is raised to above 10.5. In many cases it is preferable to maintain the pH of the feed water in the range of 10.5 to 11.5. The significance of this pH control will be subsequently addressed herein.
- Dosage of both the lime and caustic depends on the alkalinity of the feed water.
- lime will be added at the rate of about 100-300 mg/l and the caustic will be added at the rate of 300-500 mg/l.
- Other alkaline reagents such as magnesium oxide and sodium carbonate can be used.
- lime, magnesium oxide, and caustic can be added to the feed water.
- lime, soda ash and caustic are added to the feed water.
- soda ash in reactor 32 for example, to remove calcium non-carbonate hardness present in the feed water.
- reactor 34 a polymer is injected and mixed with the feed water.
- a typical polymer utilized is a cationic polymer.
- an anionic polymer can also be used in wastewater treatment applications depending on the nature of the solids contained in the wastewater.
- a typical dosage for the polymer would be about 2-5 mg/l.
- reactor 34 where the polymer is added many of the contaminants of interest will be in a precipitated form and because of the coagulant and polymer, these precipitants and solids will tend to aggregate and form floes.
- a vertical draft tube type mixer 100 Disposed in reactor 34, in one embodiment, is a vertical draft tube type mixer 100 that promotes the efficient formation of floes comprised of precipitants and suspended solids, and accordingly gives rise to crystallization and densification of these solids.
- the draft tube mixer 100 includes a tube 102 that is flared at the top and includes opposed open ends.
- a driven mixer 104 Disposed internally within the tube 102 is a driven mixer 104.
- an annular feed ring 106 Disposed above the top portion of the tube 102.
- the polymer or flocculant is fed into the annular ring 106 and the annular ring disperses the polymer or flocculant therefrom over the tube 102.
- the mixer is referred to as a down draft tube type mixer because the waste water is moved from the top of the tube 102 downwardly through the tube.
- the wastewater is continually circulated down through the tube 102 and back up outside of the tube to where the wastewater renters the top portion of the tube 102. This efficiently mixes the polymer or flocculant with the wastewater in reactor 34.
- the flow of wastewater through the tube 102 can be controlled and regulated so as to control the concentration of the polymer or flocculant added.
- the clarifier 35 comprises a settling tank, and in this embodiment, disposed over the settling tank is lamella 35A. Formed in the bottom of the settling tank is a sludge scraper. Once the feed water reaches the setting tank of the clarifier 35, solids in the form of precipitants and suspended solids will settle to the bottom of the settling tank to form sludge. Sludge is pumped from the bottom of the settling tank of the clarifier 35, with some sludge being directed through recycle line 36 back to the first reactor 31 or 32, while some portion of the sludge can be wasted through waste line 37.
- the characteristics of the produced sludge is dependent on the characteristics of the feed water being treated, such as hardness, the metals contained in the feed water, and the alkalinity of the feed water.
- the sludge will be about 60% to 70% calcium carbonate, about 20% magnesium hydroxide, and about 10% metal hydroxide compositions. Recirculation rates can vary. However, generally, at least about 5% to 10% of the feed water flow is recycled as sludge. It is contemplated that sufficient sludge is recycled to maintain approximately a 1 to 20 ratio of the dry solids generated.
- sludge from the clarifier 35 would be recycled so as to maintain about 6,000 to 12,000 mg/l of total suspended solids (TSS) in the clarifier 35.
- TSS total suspended solids
- some of the sludge would be deemed waste sludge and directed to further processing.
- the waste sludge exiting line 37 would be typically directed to a dewatering station where the sludge would be dewatered such that the dewatered sludge concentration would typically be above 35% by weight.
- the purpose of the chemical softening process described above, and which takes place in reactors 31 , 32, 33 and 34 and the clarifier 35, is to substantially reduce total hardness in the feed water to solubility limits, expressed, typically, as less than approximately 55 mg/l as CaCO 3 . Further, the softening process will, in many instances, partially remove silica. Additionally, the softening process will reduce the concentrations of soluble metals such as iron, magnesium, barium, strontium and other particulates present in the feed water. [0029] Appearing below under Table 1 is a summary of data collected from preliminary tests. Note that total hardness (expressed as CaCO 3 ) was reduced in the chemical softening process from 2100 mg/l to less than 20 mg/l. In addition, silica was reduced from 100 mg/l to 20 mg/l and the total suspended solids (TSS) were reduced from 48 mg/l to less than 20 mg/l. Importantly, pH in the chemical softening process was raised from 7.5 to 11.4.
- the chemical softening unit 30 is effective in reducing total hardness and reducing the concentration of other contaminants for several reasons.
- the reactors 31 , 32, 33 and 34 are, in a preferred embodiment, integrated with the clarifier 35.
- reactor 34 which is disposed immediately upstream from the clarifier and which receives the flocculant, includes a down draft tube mixer that effectively forms floes made up of precipitants and suspended solids and gives rise to crystallization and densification of these solids.
- the clarifier 35 including lamella 35A. All of this including the down draft tube mixer and the clarifier with lamella substantially increases the settling speed within the clarifier compared to conventional clarification systems.
- Clarified effluent leaving the clarifier 35 is directed through line 41 to the multimedia filter 40.
- a coagulant can be injected into the wastewater stream passing through line 41 prior to entry into the multimedia filter.
- the purpose of the filter is to further filter the feed water and to remove suspended and undissolved solids from wastewater.
- the function of the multimedia filter 40 is to reduce the feed water total suspended solids to less than 0.5 mg/l.
- Multimedia filter 40 is periodically backwashed with filtered water to clean the same. This backwash or waste stream is directed through line 42 to the inlet line 11 where the same is mixed with the feed water being directed into the water softening unit 30.
- Purified effluent from the multimedia filter 40 is directed through line 45 to the ion exchange unit 50.
- the function of the ion exchange unit is to further reduce the total hardness of the wastewater and to reduce the concentration of other soluble metals present in the wastewater.
- calcium and magnesium ions are removed through a process that employs a weak acid or strong acid cation resin in a sodium form.
- the recyclable waste from the ion exchange unit 50 such as backwash/compaction and fast rinse wastes, is directed through line 47 and line 42 back to the feed line 11 where the waste is mixed with the influent feed water stream. Again, portions of the waste, non- recyclable waste, from the ion exchange unit 50 such spent regenerant waste and slow rinse waste is disposed.
- the ion exchange softened water is directed from the ion exchange unit 50 through line 49 to one or more cartridge filters 60 to remove any fine particulates present in the feed water.
- An antiscalant or dispersant is added ahead of the cartridge filter to maintain a soluble chemical equilibrium across the downstream RO unit.
- Influent from the cartridge filter 60 is directed to a single pass reverse osmosis unit 70.
- Reverse osmosis unit 70 reduces organics, silica, boron, and total dissolved solids present in the wastewater.
- total hardness of the feed water is further reduced to less than approximately 0.5 mg/l (CaCOa) in the ion exchange unit 50.
- Total alkalinity of the feed water is actually increased during the chemical softening process and remains generally the same until the feed water reaches the reverse osmosis unit 70.
- the reverse osmosis unit 70 reduces the silica from 20 mg/l to less than 0.5 mg/l.
- the reverse osmosis unit 70 reduces boron from 2.6 mg/l to less than 0.1 mg/l and reduces organics from 25 mg/l to less than 0.5 mg/l.
- reverse osmosis unit 70 reduces total dissolved solids from 17,200 mg/l to less than 150 mg/l.
- Product water produced by the reverse osmosis unit 70 has a pH of 10.7. As noted in Table 1 , the pH of the wastewater being treated was actually reduced by the reverse osmosis unit 70. This is because the reverse osmosis reject stream would include carbonate and hydroxyl alkalinity that was present in the feed water.
- FIG. 1 The system shown in Figure 1 can be modified to include other subsystems or processes.
- Figure 2 illustrates a number of optional subsystems or processes that can be incorporated into the basic process described above.
- the feed water can be subjected to a degassing process prior to chemically softening the feed water.
- a degassing unit indicated generally by the numeral 80, disposed upstream from the chemical softening unit 30.
- An acid injection line 82 is provided upstream of the degassing unit 80.
- the degasification process is an optional treatment and is particularly useful for feed waters containing excess alkalinity and dissolved gases.
- an acid is injected through line 82 and mixed with the feed water to partially convert the bicarbonates present in the feed water to carbon dioxide and to maintain hydrogen sulfide or other dissolved gases in a gaseous state.
- This will effectively adjust the pH of the feed water prior to the degasification process and after the degasification process.
- the degasification process will utilize a force draft degasifier or DO x stripper so as to reduce the carbon dioxide and the hydrogen sulfide present in the feed water.
- Other types of degasifier such as vacuum or membrane or depurator type can also be used for this application.
- Degasification can be performed ahead of the chemical softening process on water with high concentrations of dissolved gases and excess bicarbonate alkalinity with the addition of acid to reduce the quantity of sludge generated and the alkali demand associated with raising the pH in the chemical softening process.
- the pH is lowered to a range of 4.5 to 6.5 ahead of the degasifier and the product water from the degasifier is typically in the pH range of 5.0 ⁇ 7.0.
- FIG. 2 Another option for the system of the present invention is the provision of dual ion exchange units.
- two ion exchange units 50 and 50' are disposed between the multimedia filter 40 and the cartridge filter 60.
- the use of the double ion exchange units 50 and 50' will serve to further reduce the hardness of the wastewater, and will particularly reduce the magnesium and carbon content of the wastewater passing therethrough.
- the application of the single or dual ion exchange units is primarily determined by the dissolved solids background of the feed water.
- the Ion Exchange system can utilize either a Strong Acid Cation Resin in Sodium form or a Weak Acid Cation Resin in Sodium Form.
- the system can be provided with dual reverse osmosis (RO) units 70 and 70'.
- RO reverse osmosis
- the present process aims to control the pH of the wastewater passing through the one or more reverse osmosis units 70 or 70' at above 10.5. This will substantially reduce organic fouling and silica scaling of the membranes in the reverse osmosis units.
- 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 which is shown in Figure 4. Note that the solubility of silica increases dramatically for pHs above 10.
- the solubility of silica at a pH of about 10.5 is almost 900 mg/l. That is to be contrasted with the solubility of silica at a pH of 8 which is about 100 mg/l.
- these scaling and fouling contaminants are maintained in solution and can be rejected by the one or more reverse osmosis units 70 or 70' without scaling and fouling.
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- Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
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Abstract
Description
Claims
Priority Applications (7)
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EP20070869141 EP2091636A4 (en) | 2006-12-12 | 2007-12-12 | Method for treating wastewater or produced water |
CA2671928A CA2671928C (en) | 2006-12-12 | 2007-12-12 | Method for treating wastewater or produced water |
CN200780051126.XA CN101646480B (en) | 2006-12-12 | 2007-12-12 | Method for treating wastewater or produced water |
MX2009006144A MX283613B (en) | 2006-12-12 | 2007-12-12 | Method for treating wastewater or produced water. |
AU2007333057A AU2007333057B8 (en) | 2006-12-12 | 2007-12-12 | Method for treating wastewater or produced water |
EA200970576A EA019136B1 (en) | 2006-12-12 | 2007-12-12 | Method for treating wastewater or produced water |
BRPI0720039A BRPI0720039B1 (en) | 2006-12-12 | 2007-12-12 | methods for treating produced water derived from a contaminant-containing oil recovery operation and for treating contaminated wastewater |
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EP (1) | EP2091636A4 (en) |
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Also Published As
Publication number | Publication date |
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MX283613B (en) | 2011-02-23 |
EP2091636A1 (en) | 2009-08-26 |
US20110023715A1 (en) | 2011-02-03 |
CA2671928C (en) | 2015-06-30 |
ZA200904023B (en) | 2010-08-25 |
CN101646480A (en) | 2010-02-10 |
US7815804B2 (en) | 2010-10-19 |
EA200970576A1 (en) | 2009-12-30 |
AU2007333057B8 (en) | 2012-11-15 |
CN101646480B (en) | 2014-01-01 |
AU2007333057B2 (en) | 2012-03-01 |
KR100951200B1 (en) | 2010-04-05 |
BRPI0720039A2 (en) | 2013-12-24 |
MX2009006144A (en) | 2009-08-26 |
BRPI0720039B1 (en) | 2018-12-26 |
AU2007333057A1 (en) | 2008-06-19 |
EA019136B1 (en) | 2014-01-30 |
CA2671928A1 (en) | 2008-06-19 |
US9067801B2 (en) | 2015-06-30 |
EP2091636A4 (en) | 2011-07-13 |
KR20080054335A (en) | 2008-06-17 |
US20080135478A1 (en) | 2008-06-12 |
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