# US 2014/0151300 A1 · Water treatment process for high salinity produced water

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- Number: US 2014/0151300 A1
- Document ID: US20140151300A1
- Status: Published application
- Kind: A1
- Application number: 13/705,445
- Filed: 2012-12-05
- Published: 2014-06-05
- Earliest claimed: 2012-12-05
- Assignees: Water & Power Technologies, Inc.
- Applicants: Water & Power Technologies, Inc.
- Inventors: Jeffrey D. Savage; Joseph C. Jimerson; Donald J. Thomas
- Web page: https://patentgrep.com/patent/US20140151300A1

## CPC

- C02F 9/00: Multistage treatment of water, waste water or sewage
- C02F 1/048: {Purification of waste water by evaporation}
- C02F 1/42: by ion-exchange (ion-exchange in general B01J)
- C02F 1/441: {by reverse osmosis}
- C02F 1/444: {by ultrafiltration or microfiltration}
- C02F 1/445: {by forward osmosis}
- C02F 1/463: by electrocoagulation
- C02F 1/66: by neutralisation; pH adjustment (for degassing C02F1/20; using ion-exchange C02F1/42; for flocculation or precipitation of suspended impurities C02F1/52; for removing dissolved compounds C02F1/58)
- C02F 5/02: Softening water by precipitation of the hardness
- C02F 11/122: using filter presses (C02F11/123 takes precedence)
- C02F 2101/101: {Sulfur compounds}
- C02F 2101/108: {Boron compounds}
- C02F 2101/16: Nitrogen compounds, e.g. ammonia
- C02F 2101/32: Hydrocarbons, e.g. oil
- C02F 2103/10: from quarries or from mining activities
- C02F 2103/365: {from petrochemical industry (e.g. refineries)}
- C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes)

## Abstract

Processes and systems for treating high salinity aqueous liquids containing dissolved minerals, suspended solids, colloidal solids, free oil and grease, dissolved organics, and dissolved hydrocarbons. The liquid is passed into an electrocoagulation system in fluid communication with a solids removal clarifier, pressurized ultrafiltration system, the draw side of forward osmosis, and a dilute draw water reverse osmosis system. Impaired water with high sulfate content is used as a source of deionized water for dilution of the forward osmosis draw solution. After concentration, the forward osmosis feed solution is further treated by lime soda softening and sludge from the softening system may be recycled to increase hardness precipitation and silica removal, the outfall from which may be treated by a separate ultrafiltration system and a feed water reverse osmosis system. Concentrate from the feed water reverse osmosis system can be treated to offer a zero liquid or near zero liquid discharge.

## Claims

### Claim 1

A method of treating an aqueous high salinity liquid containing suspended solids, colloidal solids, free oil and grease, dissolved minerals, and dissolved hydrocarbons, the method comprising:
passing an aqueous liquid containing suspended solids, colloidal solids, free oil and grease, dissolved minerals, and dissolved hydrocarbons through an electrocoagulation system at an unadjusted pH;
passing the effluent from the electrocoagulation system through an inclined plate, inclined tube, or solids contact clarifier;
passing the clarifier outfall through an ultrafiltration system; and
using the ultrafiltration filtrate as a high salinity draw solution for forward osmosis, the draw solution being diluted by deionized water drawn across a semi-permeable forward osmosis membrane by use of an impaired water as feed to the forward osmosis system prior to contacting a dilute draw water reverse osmosis system.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the impaired water used as feed to the forward osmosis system has a sulfate concentration of at least about 1,000 ppm.

### Claim 3 (depends on 2)

The method according to claim 2, wherein the impaired water used as feed to the forward osmosis system has a sulfate concentration of at least about 1,300 ppm.

### Claim 4 (depends on 2)

The method according to claim 2, further comprising treatment of concentrated feed water after forward osmosis with a lime soda softener in fluid communication with a concentrated feed water ultrafiltration system prior to contacting a high recovery concentrated feed water reverse osmosis system.

### Claim 5 (depends on 4)

The method according to claim 4, wherein treatment of the concentrated feed water after forward osmosis with a lime soda softener in fluid communication with a concentrated feed water ultrafiltration system comprises treatment of concentrated feed water lime soda precipitation softener outfall with an ultrafiltration system comprising an outside-to-inside, near dead end, hollow fiber ultrafiltration membrane module.

### Claim 6 (depends on 3)

The method according to claim 3, further comprising recycling at least a part of a precipitate sludge produced by the lime soda softener back into the lime soda softener.

### Claim 7 (depends on 2)

The method according to claim 2, further comprising blending a permeate from the dilute draw water reverse osmosis system with the permeate from the concentrated feed water reverse osmosis system to produce a combined treated water requiring pH adjustment prior to the dilute draw water reverse osmosis system to give a final permeate pH between about 6.0 and about 9.0.

### Claim 8 (depends on 7)

The method according to claim 7, further comprising remineralization of the water with the addition of a calcium salt such as calcium chloride as required to give a Sodium Adsorption Ratio (SAR) of less than about 6.

### Claim 9 (depends on 7)

The method according to claim 7, further comprising passing the combined treated water through a boron selective ion exchange system to lower the boron concentration as required to acceptable concentrations.

### Claim 10 (depends on 9)

The method according to claim 9, further comprising producing a discharge water having a sulfate concentration of less than about 450 ppm.

### Claim 11 (depends on 1)

The method according to claim 1, wherein passing the clarifier outfall through an ultrafiltration system comprises passing the clarifier outflow through an ultrafiltration system comprising a spiral wound, fouling resistant, cross flow hydrophilic membrane with corrugated feed spacer.

### Claim 12 (depends on 1)

The method according to claim 1, further comprising recycling a concentrate from the dilute draw reverse osmosis system for use in the forward osmosis draw solution.

### Claim 13 (depends on 1)

The method according to claim 1, further comprising treating a concentrate from the reverse osmosis system with an evaporator and crystallizer to create a very near liquid zero discharge, and collecting a distillate from the evaporator and crystallizer as pure water for discharge.

### Claim 14

A waste water treatment system for a high saline waste water feed stream, the system comprising:
an electrocoagulation system in fluid communication with a high saline waste water feed stream, the electrocoagulation system comprising a reaction basin with a set of vertically arranged reaction plates that are spaced apart and an electrical voltage is applied to selected members of the set of vertically arranged reaction plates by placing the selected members of the set of vertically arranged reaction plates in electrical contact with a voltage source to thereby create an electrical field within the reaction basin, and the treatment of the high saline waste water feed stream in the reaction basin takes place at unadjusted pH;
a clarifier in fluid communication with the electrocoagulation system, further feeding an ultrafiltration feed tank;
an ultrafiltration system in fluid communication with the ultrafiltration feed tank;
a forward osmosis draw solution tank in fluid communication with the filtrate from the ultrafiltration system;
a forward osmosis system in fluid communication with an impaired water used as a feed solution and the draw solution fed from the draw solution feed tank;
a forward osmosis dilute draw water reverse osmosis system in fluid communication with the forward osmosis draw solution feed tank;
a lime soda softener system in fluid communication with the forward osmosis concentrated feed water storage tank, comprising a lime and soda precipitation softener vessel;
a sludge storage tank in fluid communication with the lime and soda precipitation softener vessel, wherein contacting the forward osmosis concentrated feed water with lime and sodium carbonate (soda ash) in the lime and soda precipitation softener vessel produces a particulate suspension that settles to produce a sludge that is recycled back to the lime addition tank in fluid communication with the inlet alkalization tank prior to the lime and soda precipitation softener vessel;
a forward osmosis concentrated feed water ultrafiltration system in fluid communication with the lime and soda precipitation softener vessel;
a forward osmosis concentrated feed water reverse osmosis system in fluid communication with the forward osmosis feed water ultrafiltration system; and
a pure water discharge system in fluid combination with both reverse osmosis systems, wherein the combined high purity water may be subject to remineralization by the addition of a calcium salt such as calcium chloride in order to meet a Sodium Adsorption Ration (SAR) less than 6.

### Claim 15 (depends on 14)

The system of claim 14, wherein the electrocoagulation system comprising a reaction basin with a set of vertically arranged reaction plates that are spaced apart and an electrical voltage is applied to selected members of the set of vertically arranged reaction plates by placing the selected members of the set of vertically arranged reaction plates in electrical contact with a voltage source to thereby create an electrical field within the reaction basin further comprises a system wherein the voltage and amperage of the electrical field is adjustable by varying the selected members of the vertically arranged reaction plates that are in electrical contact with the voltage source.

### Claim 16 (depends on 14)

The system of claim 14, wherein the clarifier comprises an inclined plate, and inclined tube, or solids contact clarifier.

### Claim 17 (depends on 14)

The system of claim 14, wherein the lime soda softener system in fluid communication with the forward osmosis concentrated feed water storage tank further comprises a lime silo, lime slaker, and lime feed system; and a sodium carbonate (soda ash) silo and feed system in fluid communication with the lime and soda precipitation softener vessel.

### Claim 18 (depends on 14)

The system of claim 14, further comprising a sodium hydroxide feed ahead of the diluted draw solution reverse osmosis system for adjustment of pH to give a final combined high purity water pH between 6.0 and 9.0.

### Claim 19 (depends on 14)

The system of claim 14, further comprising a boron specific ion exchange system for reducing the boron concentration of the final combined high purity water.

### Claim 20 (depends on 14)

The system of claim 14, wherein the concentrate from the diluted forward osmosis draw solution reverse osmosis system is recycled back to the forward osmosis draw solution storage tank.

### Claim 21 (depends on 14)

The system of claim 14, further comprising an evaporator and crystallizer in fluid communication with the concentrate from the concentrated forward osmosis feed solution reverse osmosis system which treats the concentrate to create a very near liquid zero discharge for processing in a sludge handling and solids discharge system, and a distillate of pure water for discharge.