CN102701465A - Method for decalcifying sea water by using flue gas - Google Patents
Method for decalcifying sea water by using flue gas Download PDFInfo
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- CN102701465A CN102701465A CN2012101996415A CN201210199641A CN102701465A CN 102701465 A CN102701465 A CN 102701465A CN 2012101996415 A CN2012101996415 A CN 2012101996415A CN 201210199641 A CN201210199641 A CN 201210199641A CN 102701465 A CN102701465 A CN 102701465A
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Abstract
The invention discloses a method for decalcifying sea water by using flue gas, and relates to treatment of the sea water. The method comprises the following steps of: blowing the flue gas with the carbon dioxide content of 6 to 15 percent from the bottom of a reactor to the reactor filled with 500 to 1,000mL of sea water which has the calcium content of 0.40 to 1.20kg/m<3> and of which the pH value is controlled to be 7.5 to 10 at the speed of 25 to 55mL/min at the temperature of 20 to 50 DEG C, and reacting for 50 to 80 minutes, wherein through measurement, the content of calcium ions in supernatant in the reactor is 0.02 to 0.08kg/m<3>, and the decalcifying rate of the sea water in the reactor is 80.0 to 95.0 percent. The sea water is decalcified by CO2 in the waste flue gas, so that the defects that a method for decalcifying the sea water by using a chemical product is high in cost and cannot be applied on a large scale, and a method for decalcifying the sea water by using an ion exchanger is large in equipment investment and complicated in the prior art are overcome.
Description
Technical field
Technical scheme of the present invention relates to the processing of seawater, specifically carries out the method for seawater decalcification with stack gas.
Background technology
Seawater is the inorganic salt solution system of a complicacy, contain 80 altogether surplus kind of chemical element, wherein the concentration of calcium ion is 0.40kg/m
3In desalting process, the calcium salt of formation is less because of solubleness, in concentration process, can be deposited in heat transfer interface and form the calcium dirt, influences the normal operation of heat transfer efficiency and equipment; Perhaps calcium precipitation influences the life-span of film on the reverse osmosis membrane surface.Particularly after seawater concentrated above three times, lime carbonate can be separated out by mass crystallization, causes desalting process efficient sharply to descend, and then has limited the water recovery of sea water desaltination.
In the prior art, the method for seawater decalcification roughly can be divided into two types.One type is the method that adds precipitation agent, and for example: CN1778718 discloses the treatment process of softening seawater by single-decalcification, is that precipitation agent carries out crystallization with yellow soda ash, S-WAT etc. directly, softening to the seawater decalcification; CN102009987A has disclosed the brine rectification process of single stage method calcium-magnesium removing, takes off calcium-magnesium removing to add yellow soda ash.These class methods all be with chemical such as yellow soda ash or S-WATs as precipitation agent, cost is higher, sizable application can't have high input.Another kind of is absorption method or ion exchange method, and for example CN101381147 discloses sea water calcium-removing and concentrated the method for utilizing, and is to be provided with calcium-removing device at the sea water distiling plant front end, utilizes the inorganic materials of polynuclear plane to remove calcium in the seawater; CN 201210146756.8 has disclosed the method that from the rich potassium solution of seawater, removes calcium with ionite, is before the potassium enriching apparatus and before the evaporation unit, calcium-removing device to be set respectively, wherein inserts ion exchange resin.These class methods all need expensive facility investment, and operating procedure is complicated.
Summary of the invention
Technical problem to be solved by this invention is: the method for carrying out the seawater decalcification with stack gas is provided; Utilize the carbonic acid gas in the discarded stack gas to remove the calcium in the seawater as precipitation agent, overcome cost height that the chemical that needs the cost funds to buy in the prior art removes the calcium in the seawater can't have high input sizable application and with ionite remove the facility investment of the calcium in the seawater expensive with the complicated shortcoming of operating procedure.
The present invention solves this technical problem the technical scheme that is adopted: the method for carrying out the seawater decalcification with stack gas; Its operating procedure is: in temperature is under 20 ℃～50 ℃ conditions, with carbon dioxide content be 6～15% stack gas blast with the speed of 25mL/min～55mL/min from reactor bottom that 500mL～1000mL calcium content is housed is 0.40 kg/m
3～1.20kg/m
3The pH value be controlled in the reactor drum of 7.5～10 seawater, behind reaction 50～80 min, the content of the calcium ion in the supernatant in the assaying reaction device is 0.02kg/m
3～0.08 kg/m
3, the decalcification rate of the seawater in the reactor drum is 80.0～95.0%.
Above-mentioned method of carrying out the seawater decalcification with stack gas; Said pH value control is to control the drop rate of alkali lye so that the pH value of the seawater in the reactor drum remains on 7.5～10 with combined electrode and pH meter, and the add-on of alkali lye is confirmed by combined electrode controlled on-line pH value automatically.
Above-mentioned method of carrying out the seawater decalcification with stack gas, said alkali lye are that volumetric molar concentration is the aqueous sodium hydroxide solution of 1mol/L～4mol/L.
Above-mentioned method of carrying out the seawater decalcification with stack gas; The said speed that blasts the stack gas of reactor bottom be with reactor drum in the volume of seawater become the forward ratio with calcium content; After reacting 50～80 min, the content of the calcium ion in the supernatant in the reactor drum is 0.02kg/m with the stack gas that guarantees to blast reactor drum and the seawater in the reactor drum
3～0.08 kg/m
3, the decalcification rate of the seawater in the reactor drum is 80.0～95.0%.
Above-mentioned method of carrying out the seawater decalcification with stack gas, related equipment and raw material all obtain through the known approach of present technique field institute, used operating procedure be the present technique field the technician knew.
The invention has the beneficial effects as follows: compared with prior art, the obvious improvement that the present invention carries out the method for seawater decalcification with stack gas is:
(1) reduces the cost that has brine disposal now
The inventive method as precipitation agent, substitutes yellow soda ash and one type of chemical of S-WAT as precipitation agent with the carbonic acid gas in the waste gas stack gas, has reduced the raw materials cost of brine disposal significantly; With expensive the comparing of facility investment that removes the calcium in the seawater with ionite, the simple valency of the equipment of the inventive method is low.The inventive method reduces the cost of existing brine disposal in a word.
(2) the water recovery of lifting sea water desaltination
Use the inventive method, the decreasing ratio of calcium can reach more than 90% in the seawater, has promoted the water recovery of sea water desaltination significantly.
(3) turn waste into wealth environmental protection
The inventive method sizable application that has high input can purify dead flue gas, realizes turning waste into wealth, and reduces the discharging of greenhouse gases.
Embodiment
Embodiment 1
In temperature is under 20 ℃ of conditions, with carbon dioxide content be 6% stack gas blast with the speed of 25mL/min from reactor bottom that the 500mL calcium content is housed is 0.40kg/m
3The pH value be controlled in the reactor drum of 7.5 seawater, react 80 min after, the content of the calcium ion in the supernatant in the assaying reaction device is 0.08 kg/m
3, the decalcification rate of the seawater in the reactor drum is 80.0%.Said pH value control is to control the drop rate of alkali lye so that the pH value of the seawater in the reactor drum remains on 7.5 with combined electrode and pH meter, and the add-on of alkali lye is confirmed by combined electrode controlled on-line pH value automatically.
Embodiment 2
In temperature is under 50 ℃ of conditions, with carbon dioxide content be 15% stack gas blast with the speed of 35mL/min from reactor bottom that the 1000mL calcium content is housed is 0.40kg/m
3The pH value be controlled in the reactor drum of 8 seawater, react 70 min after, the content of the calcium ion in the supernatant in the assaying reaction device is 0.06kg/m
3, the decalcification rate of the seawater in the reactor drum is 85.0%.Said pH value control is to control the drop rate of alkali lye so that the pH value of the seawater in the reactor drum remains on 8 with combined electrode and pH meter, and the add-on of alkali lye is confirmed by combined electrode controlled on-line pH value automatically.
Embodiment 3
In temperature is under 30 ℃ of conditions, with carbon dioxide content be 15% stack gas blast with the speed of 45mL/min from reactor bottom that the 750mL calcium content is housed is 0.80kg/m
3The pH value be controlled in the reactor drum of 9.0 seawater, react 60 min after, the content of the calcium ion in the supernatant in the assaying reaction device is 0.08kg/m
3, the decalcification rate of the seawater in the reactor drum is 90.0%.Said pH value control is to control the drop rate of alkali lye so that the pH value of the seawater in the reactor drum remains on 9.0 with combined electrode and pH meter, and the add-on of alkali lye is confirmed by combined electrode controlled on-line pH value automatically.
Embodiment 4
In temperature is under 25 ℃ of conditions, with carbon dioxide content be 13% stack gas blast with the speed of 25mL/min from reactor bottom that the 500mL calcium content is housed is 0.40kg/m
3The pH value be controlled in the reactor drum of 10 seawater, behind the reaction 50min, the content of the calcium ion in the supernatant in the assaying reaction device is 0.02kg/m
3, the decalcification rate of the seawater in the reactor drum is 95.0%.Said pH value control is to control the drop rate of alkali lye so that the pH value of the seawater in the reactor drum remains on 10 with combined electrode and pH meter, and the add-on of alkali lye is confirmed by combined electrode controlled on-line pH value automatically.
Embodiment 5
In temperature is under 25 ℃ of conditions, with carbon dioxide content be 13% stack gas blast with the speed of 55mL/min from reactor bottom that the 1000mL calcium content is housed is 1.20kg/m
3The pH value be controlled in the reactor drum of 8 seawater, behind the reaction 60min, the content of the calcium ion in the supernatant in the assaying reaction device is 0.08kg/m
3, the decalcification rate of the seawater in the reactor drum is 93.3%.Said pH value control is to control the drop rate of alkali lye so that the pH value of the seawater in the reactor drum remains on 8 with combined electrode and pH meter, and the add-on of alkali lye is confirmed by combined electrode controlled on-line pH value automatically.
In the foregoing description, related equipment and raw material all obtain through the known approach of present technique field institute, used operating procedure be the present technique field the technician knew.
Claims (4)
1. carry out the method for seawater decalcification with stack gas; It is characterized in that operating procedure is: in temperature is under 20 ℃～50 ℃ conditions, with carbon dioxide content be 6～15% stack gas blast with the speed of 25mL/min～55mL/min from reactor bottom that 500mL～1000mL calcium content is housed is 0.40 kg/m
3～1.20kg/m
3The pH value be controlled in the reactor drum of 7.5～10 seawater, behind reaction 50～80 min, the content of the calcium ion in the supernatant in the assaying reaction device is 0.02kg/m
3～0.08 kg/m
3, the decalcification rate of the seawater in the reactor drum is 80.0～95.0%.
2. according to the said method of carrying out the seawater decalcification with stack gas of claim 1; It is characterized in that: said pH value control is to control the drop rate of alkali lye so that the pH value of the seawater in the reactor drum remains on 7.5～10 with combined electrode and pH meter, and the add-on of alkali lye is confirmed by combined electrode controlled on-line pH value automatically.
3. according to the said method of carrying out the seawater decalcification with stack gas of claim 2, it is characterized in that: said alkali lye is that volumetric molar concentration is the aqueous sodium hydroxide solution of 1mol/L～4mol/L.
4. according to the said method of carrying out the seawater decalcification with stack gas of claim 1; It is characterized in that: the volume of the seawater in the speed of the said stack gas that blasts reactor bottom and the reactor drum becomes the forward ratio with calcium content; After reacting 50～80 min, the content of the calcium ion in the supernatant in the reactor drum is 0.02kg/m with the stack gas that guarantees to blast reactor drum and the seawater in the reactor drum
3～0.08 kg/m
3, the decalcification rate of the seawater in the reactor drum is 80.0～95.0%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553246A (en) * | 2013-11-21 | 2014-02-05 | 武汉森泰环保工程有限公司 | Device and method for softening hard water by using carbon dioxide in flue gas |
| CN103990370A (en) * | 2014-06-06 | 2014-08-20 | 天津滨瀚环保科技发展有限公司 | Method for reducing emission of thermal power generation smoke CO2 and subsidiarily producing superfine nanometer CaCO3 from thermal power generation smoke CO2 |
| CN104108803A (en) * | 2014-06-30 | 2014-10-22 | 河北工业大学 | New method for removing calcium from seawater through flue gas carbon sequestration |
| CN104291452A (en) * | 2014-07-02 | 2015-01-21 | 中国石油天然气集团公司 | Flue gas hardness reducing apparatus and use method thereof |
| CN107487869A (en) * | 2017-09-12 | 2017-12-19 | 江苏天楹环保能源成套设备有限公司 | A kind of device for preventing landfill leachate treatment equipment scaling |
| CN105712452B (en) * | 2014-12-05 | 2019-03-19 | 中国石油化工股份有限公司 | A method of calcium ion in removal epoxychloropropane waste water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3923607A (en) * | 1972-08-10 | 1975-12-02 | Hisanobu Tabata | Process for pretreating sea water by preheating same in the preparation of brine and fresh water |
| CN2226486Y (en) * | 1995-10-11 | 1996-05-08 | 彭斯干 | Industrial smoke seawater washer |
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2012
- 2012-06-18 CN CN 201210199641 patent/CN102701465B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923607A (en) * | 1972-08-10 | 1975-12-02 | Hisanobu Tabata | Process for pretreating sea water by preheating same in the preparation of brine and fresh water |
| CN2226486Y (en) * | 1995-10-11 | 1996-05-08 | 彭斯干 | Industrial smoke seawater washer |
Non-Patent Citations (1)
| Title |
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| 张继军 等: "利用CO_2脱除海水中的钙离子和镁离子", 《化工进展》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553246A (en) * | 2013-11-21 | 2014-02-05 | 武汉森泰环保工程有限公司 | Device and method for softening hard water by using carbon dioxide in flue gas |
| CN103990370A (en) * | 2014-06-06 | 2014-08-20 | 天津滨瀚环保科技发展有限公司 | Method for reducing emission of thermal power generation smoke CO2 and subsidiarily producing superfine nanometer CaCO3 from thermal power generation smoke CO2 |
| CN104108803A (en) * | 2014-06-30 | 2014-10-22 | 河北工业大学 | New method for removing calcium from seawater through flue gas carbon sequestration |
| CN104108803B (en) * | 2014-06-30 | 2015-10-28 | 河北工业大学 | A kind of method of flue gas-solid carbon seawater decalcification |
| CN104291452A (en) * | 2014-07-02 | 2015-01-21 | 中国石油天然气集团公司 | Flue gas hardness reducing apparatus and use method thereof |
| CN105712452B (en) * | 2014-12-05 | 2019-03-19 | 中国石油化工股份有限公司 | A method of calcium ion in removal epoxychloropropane waste water |
| CN107487869A (en) * | 2017-09-12 | 2017-12-19 | 江苏天楹环保能源成套设备有限公司 | A kind of device for preventing landfill leachate treatment equipment scaling |
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| CN102701465B (en) | 2013-09-04 |
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