WO2007094691A1 - Method for handling saline water and carbon dioxide - Google Patents

Method for handling saline water and carbon dioxide Download PDF

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Publication number
WO2007094691A1
WO2007094691A1 PCT/NO2007/000062 NO2007000062W WO2007094691A1 WO 2007094691 A1 WO2007094691 A1 WO 2007094691A1 NO 2007000062 W NO2007000062 W NO 2007000062W WO 2007094691 A1 WO2007094691 A1 WO 2007094691A1
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Prior art keywords
carbon dioxide
ammonia
ammonium
water
chloride
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PCT/NO2007/000062
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French (fr)
Inventor
Omar Chaalal
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Enpro As
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Publication of WO2007094691A1 publication Critical patent/WO2007094691A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/18—Preparation by the ammonia-soda process
    • 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
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C02F1/265—Desalination
    • 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
    • C02F2103/08—Seawater, e.g. for desalination
    • 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
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a method for handling of water containing an amount of salt, according to the preamble of claim 1.
  • the invention also relates to applications of the method.
  • the main object of the invention is to achieve a method and a novel technique for transforming brine water which is discharged or rejected from desalination plants into a useful irrigation water and soda ash compounds (NaaCOs).
  • the problem is caused by the fact that the concentration of salt in the sea to which the salt is discharged, increases in areas of shallow seas.
  • An object of the invention is to provide for a process enabling operators of power plants, such as gasworks, to remove and recover emissions of carbon dioxide in exhaust gas.
  • the method of the present invention is characterised in that carbon dioxide is combined with an alkaline solution based on ammonia, for the formation of ammonium bicarbonates, said bicarbonates being further reacted with a saline comprising solution, forming products of alkaline metal bicarbonate and ammonium chloride, and said ammonium chloride product is processed further in a decomposition to form ammonia and hydrochloric acid, and said ammonia chloride is returned to the first step forming said alkaline solution with water, while the alkaline metal bicarbonate is optionally further decomposed into carbon dioxide which is returned to the first step of the method.
  • the saline containing solution is a sodium chloride containing solution, and preferably it is a brine, such as a salty NaCI-solution, originating from a desalination plant.
  • the ammonium chloride part is heated to decompose into ammonia, while the hydro chloride part from the decomposition, may be deposited.
  • the carbon dioxide needed for the process is taken from: a) exhaust gas from combustion processes, b) a process of regenerating monoethanolamine, c) from decomposition of said alkaline metal bicarbonate, or is used in a mixture thereof.
  • the alkaline metal bicarbonate and said carbon dioxide is formed by heating an alkaline metal carbonate in a calcinater, such as in a rotary furnace.
  • the ammonium bicarbonate NH 4 HCO 3 is produced in two steps, the first being that carbon dioxide is combined with the alkaline solution in step 1a forming ammonium carbonate (NH 4 ) 2 CO 3 , which is then reacted with more carbon dioxide and water to form said ammonium bicarbonateNH 4 HCO 3 .
  • step 1) a) formation of ammonium carbonate (NH 4 ) 2 CO 3 by the reaction:
  • step 2) reacting ammonium hydrogen carbonate of step 1b) with brine water to form ammonium chloride and sodium-bicarbonate
  • step 3 converting the dry sodium bicarbonate by heating to give anhydrite sodium carbonate or soda ash:
  • the method of the invention is used for handling of brine water originating from a desalination plant, said brine being added to the process of step 2, or for removing carbon dioxide from combustion gas, such as related to power plants driven by the combusting of coal, oil or gas.
  • the method is used for removing carbon dioxide from industrial activity, such as in smelting plants causing considerable emissions of carbon dioxide in their exhaust gases.
  • the inventive method is used in a combined process for removing carbon dioxide from combustion gases and for a simultaneous desalination of water.
  • the novel technique according to the invention uses a new and revised version of the old Solway process.
  • the carbon dioxide is derived from any CO 2 containing exhaust gas originating from a combustion process, or the carbon dioxide originates from the regeneration of monoethanolamine.
  • the old and well known Solway process use is made of calcium carbonate (CaCOs) and sodium chloride (NaCI), while in the new revised version of Solway process there is no need for using calcium carbonate.
  • the carbon dioxide needed is taken from exhaust gases or from the exhaust of the regeneration of monoethanolamine used in natural gas processing.
  • the ammonium chloride (NH 4 CI) from the process is heated then it sublimates or decompose to give ammonia (NH 3 ) and hydrochloric acid (HCI).
  • the recovered ammonia is recycled in return to the initial brine solution.
  • step 2 the ammonium hydrogen carbonate of step b) is reacted with the rejected brine water coming from a desalination plant to form sodium bicarbonate
  • step 3 the NaHCO 3 Js converted into Na 2 CO 3 .
  • the carbon dioxide CO 2 may be returned to step 1
  • the sodium carbonate Na 2 CO 3 precipitates and may put to the market.
  • the ammonium chloride is heated to decompose to give ammonia and hydrochloric acid.
  • the ammonia is returned to sub step a).
  • step 2 The product compounds NaHCO 3 and NH 4 CI of step 2), represents the same compounds which are formed according to the Solway Process.
  • ammonia chloride is reacted with lime under heating forming ammonia, calcium oxide and water, as follows:
  • this step is not necessary since ammonia chloride NH 4 CI is decomposed into NH 3 and HCI, and the NH 3 is returned to step 1.
  • Said CaO is normally produced by heating of calcium carbonate CaCO 3 as follows:
  • the CO 2 produced here is the extra CO 2 produced so that there is no net use of CO 2 in the standard process.
  • the CaO (calcium oxide) is a very strong and corrosive base, and so it is hard to work with and must be generated there and then.
  • the ammonia compound NH 3 is recirculated from step 4 to step 1.
  • the need for a supply of fresh ammonia may be completely eliminated or highly reduced.
  • the supply of CO 2 comes from the exhaust gas, and from the regeneration of said monoethanolamine used in the natural gas processing.
  • the reactions according to steps 1 and 2 are conducted.
  • the carbon dioxide from exhaust gases or MEA from regeneration in C, is conducted into reactor D through line 10.
  • Brine water from A is led into the reactor top D through line 12.
  • Water for irrigation purposes are conducted through line 14 to storage F.
  • step 1 and 2 ammonia chloride and soda ash are separated in 20 conducting the ammonia chloride product into E, while the soda ash (NaHCOs) is led through line 22 into box 30, and further heated to decompose into CO2 (at 32) which is returned to the section C, the total CO 2 source of the process.
  • soda ash NaHCOs
  • ammonia NH 3 produced in section E is further conducted through line 34 to section C to form an ammonia solution (in water).
  • This solution is further led to Section A which contains an aqueous brine solution originating from a desalination plant.
  • This brine solution is conducted through line 12 to the reactor top.
  • the major advantages of the present invention is that: -the rejection or dumping of brine water may be eliminated in that the sodium chloride may be used as an reactant in the process, -carbon dioxide gases in combustion exhaust gases may optionally be consumed and eliminated.
  • the reactant ammonia (NH 3 ) may be circulated in the process, -there is no need to incorporate any calcium carbonate in the process as is done in the Solway process.

Abstract

There is disclosed at method for conducting a reaction, which is characterised in that carbon dioxide is combined with an alkaline solution based on ammonia, for the formation of ammonium bicarbonates, said bicarbonates being further reacted with a saline comprising solution, forming products of alkaline metal bicarbonate and ammonium chloride, and said ammonium chloride product is processed further in a decomposition to form ammonia and hydro chloric acid, and said ammonia chloride is returned to the first step forming said alkaline solution with water, while the alkaline metal bicarbonate is optionally further decomposed into carbon dioxide which is returned to the first step of the method. According to another aspect, the invention is used for handling of brine water originating from a desalination plant, for removing carbon dioxide from combustion gas, such as related to power plants or other industrial activities. Preferably the method is used in a combined process for removing carbon dioxide from combustion gas and desalination of water.

Description

Method for handling saline water and carbon dioxide.
The present invention relates to a method for handling of water containing an amount of salt, according to the preamble of claim 1. The invention also relates to applications of the method.
More precise the main object of the invention is to achieve a method and a novel technique for transforming brine water which is discharged or rejected from desalination plants into a useful irrigation water and soda ash compounds (NaaCOs).
The huge amount of brine water which is discharged, rejected or dumped in the sea during desalination plants, is a real pollution problem. The problem is caused by the fact that the concentration of salt in the sea to which the salt is discharged, increases in areas of shallow seas.
For areas such as the gulf regions this is considered to be an increasing problem in the near future. If not solved this soon the shallow sea water will be transformed to brine water more the less.
Reference is made to Norwegian patent document No. 319.666 which discloses the removal of carbon dioxide CO2 of exhaust gases by reacting with sea water. NH4CI is a resulting product by this process decomposing into ammonia NH3 + and chloride Cl". US-patent publication No. 1 ,570,299 discloses the well known Solway processen.
An object of the invention is to provide for a process enabling operators of power plants, such as gasworks, to remove and recover emissions of carbon dioxide in exhaust gas. The method of the present invention is characterised in that carbon dioxide is combined with an alkaline solution based on ammonia, for the formation of ammonium bicarbonates, said bicarbonates being further reacted with a saline comprising solution, forming products of alkaline metal bicarbonate and ammonium chloride, and said ammonium chloride product is processed further in a decomposition to form ammonia and hydrochloric acid, and said ammonia chloride is returned to the first step forming said alkaline solution with water, while the alkaline metal bicarbonate is optionally further decomposed into carbon dioxide which is returned to the first step of the method.
According to a preferred option, the saline containing solution is a sodium chloride containing solution, and preferably it is a brine, such as a salty NaCI-solution, originating from a desalination plant.
The ammonium chloride part is heated to decompose into ammonia, while the hydro chloride part from the decomposition, may be deposited.
According to a preferred embodiment, the carbon dioxide needed for the process is taken from: a) exhaust gas from combustion processes, b) a process of regenerating monoethanolamine, c) from decomposition of said alkaline metal bicarbonate, or is used in a mixture thereof.
According to a preferred embodiment, the alkaline metal bicarbonate and said carbon dioxide is formed by heating an alkaline metal carbonate in a calcinater, such as in a rotary furnace.
According to a another preferred embodiment , the ammonium bicarbonate NH4HCO3 is produced in two steps, the first being that carbon dioxide is combined with the alkaline solution in step 1a forming ammonium carbonate (NH4)2CO3, which is then reacted with more carbon dioxide and water to form said ammonium bicarbonateNH4HCO3.
In a further preferred option, the reaction is conducted by the following steps: step 1): a) formation of ammonium carbonate (NH4)2CO3 by the reaction:
NH3 + CO2 +H2O => (NH4)2CO3, D) transforming (NH4)2CO3 to 2NH4HCO3 by any excess of CO2 : (NhU)2CO3 + CO2 + H2O => 2NH4HCO3 (aq.), step 2): reacting ammonium hydrogen carbonate of step 1b) with brine water to form ammonium chloride and sodium-bicarbonate
NH4HCO3 + NaCI => NaHCO3 + NH4CI, step 3): converting the dry sodium bicarbonate by heating to give anhydrite sodium carbonate or soda ash:
NH4HCO3 heat => Na2CO3 + NH4CI + CO2 + H2O, wherein the carbon dioxide CO2 may be returned to steps 1a) and 1b), and
step 4): heating the ammonium chloride to decompose to give ammonia and hydrochloric acid,
NH4CI => NH3 + HCI, and that said ammonia is returned to step 1 a).
The preferred features of the method appear in the independent claims 2-9.
According to the invention the method of the invention is used for handling of brine water originating from a desalination plant, said brine being added to the process of step 2, or for removing carbon dioxide from combustion gas, such as related to power plants driven by the combusting of coal, oil or gas.
According to another preferred use, the method is used for removing carbon dioxide from industrial activity, such as in smelting plants causing considerable emissions of carbon dioxide in their exhaust gases.
Most preferred the inventive method is used in a combined process for removing carbon dioxide from combustion gases and for a simultaneous desalination of water.
The novel technique according to the invention, uses a new and revised version of the old Solway process. In the present process of the invention the carbon dioxide is derived from any CO2 containing exhaust gas originating from a combustion process, or the carbon dioxide originates from the regeneration of monoethanolamine. In the old and well known Solway process, use is made of calcium carbonate (CaCOs) and sodium chloride (NaCI), while in the new revised version of Solway process there is no need for using calcium carbonate.
The carbon dioxide needed is taken from exhaust gases or from the exhaust of the regeneration of monoethanolamine used in natural gas processing. The ammonium chloride (NH4CI) from the process is heated then it sublimates or decompose to give ammonia (NH3) and hydrochloric acid (HCI). The recovered ammonia is recycled in return to the initial brine solution.
The following is a detailed disclosure of the method of the invention
Step i
An ammonia solution is combined with the carbon dioxide CO2 coming from the sources mentioned above in two sub steps a) and b):
a) formation of ammonium carbonate (NH4^CO3
NH3 + CO2 +H2O => (NH4)2CO3
b) any excess of CO2 will transform (NH4)2CO3 to 2NH4HCO3 (ammoniumhydrogencarbonate) as follows.
(NH-O2CO3 + CO2 + H2O => 2NH4HCO3 (aq.)
Step 2
In step 2 the ammonium hydrogen carbonate of step b) is reacted with the rejected brine water coming from a desalination plant to form sodium bicarbonate
NH4HCO3 + NaCI => NaHCO3 + NH4CI
Step 3
In step 3, the NaHCO3 Js converted into Na2CO3.
Dry sodium bicarbonate is heated in a rotary furnace (CALCINATER) the gives anhydrite sodium carbonate or soda ash as follows:.
NH4HCO3 heat => Na2CO3 + NH4CI + CO2 + H2O.
The carbon dioxide CO2 may be returned to step 1 The sodium carbonate Na2CO3 precipitates and may put to the market.
Step 4
According to the invention, the ammonium chloride is heated to decompose to give ammonia and hydrochloric acid. The ammonia is returned to sub step a).
NH4CI => NH3 + HCI
The product compounds NaHCO3 and NH4CI of step 2), represents the same compounds which are formed according to the Solway Process.
However, in the Solway Process, the ammonia chloride is reacted with lime under heating forming ammonia, calcium oxide and water, as follows:
NH4CI + CaO => NH3 + CaCI2 + H2O
In the present invention however, this step is not necessary since ammonia chloride NH4CI is decomposed into NH3 and HCI, and the NH3 is returned to step 1.
Thus the present invention eliminates the step of producing said CaO of the Solway process. Said CaO is normally produced by heating of calcium carbonate CaCO3 as follows:
CaCO3 => CO2 + CaO.
The CO2 produced here, is the extra CO2 produced so that there is no net use of CO2 in the standard process.
For step 4 of the Solway process, the CaO (calcium oxide) is a very strong and corrosive base, and so it is hard to work with and must be generated there and then.
Step 2 above represents the standard Solway process (= ammonia- soda process), but usually CO2 used is recycled from the standard step 4, so there is no net use of CO2, and it cannot be used fro removing CO2 fro exhaust/MEA, where only half of the CO2 is recycled. Thus, according to the invention, the ammonia compound NH3 is recirculated from step 4 to step 1. Thus the need for a supply of fresh ammonia may be completely eliminated or highly reduced.
Further, the supply of CO2 comes from the exhaust gas, and from the regeneration of said monoethanolamine used in the natural gas processing.
The invention shall be explained further by reference to the figure 1 in which the elements of the process plant are numbered as follows.
A : Brine water from desalination plant
B : Ammonia solution
C : Carbon Dioxide from exhaust gases or MEA regeneration
D: Solvay tower (reactor)
E: recycled ammonia
F : water irrigation storage.
In the Solway tower D, the reactions according to steps 1 and 2 are conducted. The carbon dioxide from exhaust gases or MEA from regeneration in C, is conducted into reactor D through line 10. Brine water from A is led into the reactor top D through line 12. Water for irrigation purposes are conducted through line 14 to storage F.
The products of step 1 and 2 ammonia chloride and soda ash are separated in 20 conducting the ammonia chloride product into E, while the soda ash (NaHCOs) is led through line 22 into box 30, and further heated to decompose into CO2 (at 32) which is returned to the section C, the total CO2 source of the process.
The ammonia NH3 produced in section E is further conducted through line 34 to section C to form an ammonia solution (in water). This solution is further led to Section A which contains an aqueous brine solution originating from a desalination plant.
This brine solution is conducted through line 12 to the reactor top.
The major advantages of the present invention is that: -the rejection or dumping of brine water may be eliminated in that the sodium chloride may be used as an reactant in the process, -carbon dioxide gases in combustion exhaust gases may optionally be consumed and eliminated.
-the reactant ammonia (NH3) may be circulated in the process, -there is no need to incorporate any calcium carbonate in the process as is done in the Solway process.

Claims

P A T E N T C L A I M S
1. A method for conducting a reaction, characterised in that carbon dioxide is combined with an alkaline solution based on ammonia, for the formation of ammonium bicarbonates, said bicarbonates being further reacted with a saline comprising solution, forming products of alkaline metal bicarbonate and ammonium chloride, and said ammonium chloride product is processed further in a decomposition to form ammonia and hydro chloric acid, and said ammonia chloride is returned to the first step forming said alkaline solution with water, while the alkaline metal bicarbonate is optionally further decomposed into carbon dioxide which is returned to the first step of the method.
2. Method according to claim 1 , characterised in that the saline containing solution is a sodium chloride containing solution.
3. Method according to claim 1-2, characterised in that the saline containing solution is a brine, such as a salty NaCI-solution, originating from a desalination plant.
4. Method according to claim 1-3, characterised in that said ammonium chloride is heated to decompose into ammonia.
5. Method according to claim 1-4, characterised in that the hydro chloride part from the decomposition, is deposited.
6. Method according to any of preceding claims, characterised in that the carbon dioxide needed for the process originates from a) exhaust gas from combustion processes, b) a process of regenerating monoethanolamine, c) from decomposition of said alkaline metal bicarbonate, or a mixture thereof.
7. Method according to any of claims 1-6, characterised in that said alkaline metal bicarbonate and said carbon dioxide is formed by heating an alkaline metal carbonate in a calcinater, such as in a rotary furnace.
8. Method according to any of preceding claims, characterised in that the ammonium bicarbonate NH4HCO3 is produced in two steps, the first being that carbon dioxide is combined with the alkaline solution in step 1a forming ammonium carbonate (NH4)2CO3, which is then reacted with more carbon dioxide and water to form said ammonium bicarbonateN H4HCO3.
9. Method according to any of the preceding claims, characterised in that the reaction is conducted by the following steps:
step 1): a) formation of ammonium carbonate (NH4)2CO3 by the reaction:
NH3 + CO2 +H2O => (NH4)2CO3, b) transforming (NH4)2CO3 to 2NH4HCO3 by any excess of CO2 :
(NH-O2CO3 + CO2 + H2O => 2NH4HCO3 (aq.), step 2): reacting ammonium hydrogen carbonate of step 1b) with brine water to form ammonium chloride and sodium-bicarbonate
NH4HCO3 + NaCI => NaHCO3 + NH4CI, step 3): converting the dry sodium bicarbonate by heating to give anhydrite sodium carbonate or soda ash:
NH4HCO3 heat => NaCO3 + NH4CI + CO2 + H2O, wherein the carbon dioxide CO2 may be returned to steps 1a) and 1b), and step 4): heating the ammonium chloride to decompose to give ammonia and hydrochloric acid,
NH4CI => NH3 + HCI, and that said ammonia is returned to step 1 a).
10. Use of the method according to any of the preceding claims, for handling of brine water originating from a desalination plant, said brine being added to the process of step 2.
11. Use of the method according to any of the preceding claims, for removing carbon dioxide from combustion gas, such as related to power plants driven by the combusting of coal, oil or gas.
12. Use of the method according to any of the preceding claims, for removing carbon dioxide from industrial activity.
13. Use of the method according to any of the preceding claims, in combined process for removing carbon dioxide from combustion gas and desalination of water.
PCT/NO2007/000062 2006-02-17 2007-02-16 Method for handling saline water and carbon dioxide WO2007094691A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20060807A NO20060807L (en) 2006-02-17 2006-02-17 Process for the purification of saline water
NO20060807 2006-02-17

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