WO2000041967A1 - Ammonia recovery - Google Patents
Ammonia recovery Download PDFInfo
- Publication number
- WO2000041967A1 WO2000041967A1 PCT/AU2000/000014 AU0000014W WO0041967A1 WO 2000041967 A1 WO2000041967 A1 WO 2000041967A1 AU 0000014 W AU0000014 W AU 0000014W WO 0041967 A1 WO0041967 A1 WO 0041967A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ammonia
- process according
- reaction slurry
- milling means
- milling
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
- C01C1/028—Preparation of ammonia from inorganic compounds from ammonium sulfate or sulfite
Definitions
- the present invention relates to ammonia recovery. More particularly, the present invention relates to a process for the recovery of ammonia from ammonium sulphate solutions or ammonium sulphate containing wastewater streams.
- ammonia In many mineral processing and chemical applications, ammonia is widely used for its mild alkaline characteristics, ease of use, and potential ability to be recycled. For example, in the mineral processing industry, ammonia is used in the ammoniacal leaching, nickel/cobalt hydrogen reduction, and nickel/cobalt solvent extraction processes.
- ammonia is recovered from solutions of ammonium sulphate by reacting the ammonium sulphate solution with milk of lime (hydrated calcium oxide or hydrated/slaked lime) in a stirred tank, referred to as a "lime boil".
- the hydrated lime (Ca(OH) 2 ) is typically produced by reacting quicklime (CaO) with water in a "slaker” or similar device.
- the milk of lime is then added to the ammonia recovery system.
- the lime utilised in this process must be hydrated prior to addition to the lime boil as gypsum (CaS0 4 .2H 2 0) is formed during the process.
- the gypsum thus formed coats the quicklime and consequently there is very poor utilisation of quicklime in the process.
- ammonium sulphate reacts with the milk of lime
- ammonia is liberated by the reaction of the ammonium ion with the hydroxide ions in the milk of lime, and the insoluble gypsum is formed as a reaction product.
- the ammonia is stripped off the slurry by heating to about 90 to 100°C by the addition of steam.
- the off- gases from the process contain both ammonia and water vapour.
- the ammonia is able to be recovered in a relatively pure form as a solution of ammonia in water by cooling the off-gases.
- the consumption of lime in this process is often significantly higher than that predicted by the stoichiometry of the chemical reactions taking place, usually 10 to 50% higher.
- This is a product of the fact that the gypsum formed in the process has a tendency to coat any particles of unreacted lime. This restricts further reactions with any underlying lime particles that may not be fully hydrated.
- the gypsum further tends to precipitate on the inside of the tank, on the agitator, and any internal pipe work such as the steam injection pipes. These precipitates can be so severe as to interfere with the continuous operation of the process and significant periods can be spent removing precipitate. There have been instances where lime boil plants have been shut down due to the inability to effectively operate this process.
- ammonia regeneration/recovery can be a critical process both technically and economically.
- the process for recovery of ammonia from ammonia sulphate solution of the present invention has as one object thereof to overcome at least in part the above problems associated with the prior art.
- the reaction slurry generates heat through the slaking of the quicklime.
- the process of the present invention may further comprise the additional method step of injecting air or steam into the reaction slurry to strip liberated ammonia therefrom.
- the milling means is provided in the form of a ball mill. Still preferably, the air or steam is injected continuously into the reaction slurry whilst in the milling means.
- the ball mill has a non-rotary action
- the ball mill may be in the form of a vibrating mill In such a mill the charge therein is mobile at all times and its shell does not rotate, thereby allowing the mill to be gas-tight
- the process of the present invention preferably also comprises the method step of condensing off-gases from the reaction slurry and recovering ammonia as ammonia solution
- the off-gases may be recovered from the milling means or from another reaction or stripping vessel depending upon where the stripping of ammonia takes place
- the process of the present invention may further comprise the additional method step of boiling the air or steam stripped discharge slurry or filtrate to recover at least a portion of any remaining ammonia.
- Ammonium sulphate solution from which it is desired to recover ammonia, is mixed with quicklime (CaO) at ambient temperature in a milling means, for example a ball mill adapted for the purpose, to provide a reaction slurry
- a milling means for example a ball mill adapted for the purpose, to provide a reaction slurry
- a ball mill with a non-rotary action is preferred as the charge is mobile at all times and the shell does not rotate, thereby allowing the mill to be gas-tight.
- Air or steam is continuously injected into the reaction slurry in the ball mill during operation and strips liberated ammonia therefrom It is envisaged that the reaction slurry may be transferred to another vessel, possibly termed a stripping vessel, in which the stripping of liberated ammonia may be conducted Off- gases produced by the reaction slurry are condensed and ammonia recovered as ammonia solution.
- a stripping vessel in which the stripping of liberated ammonia may be conducted Off- gases produced by the reaction slurry are condensed and ammonia recovered as ammonia solution.
- the action of the charge or balls in the ball mill acts to continuously break up any gypsum (CaS0 4 .2H 2 0) precipitate as it forms during the ammonia recovery process.
- the breaking up of the gypsum precipitate in this manner exposes fresh quicklime surfaces allowing for further reaction with the ammonium sulphate solution and prevents gypsum scale formation inside the mill and associated pipe work.
- the slaking of the quicklime that occurs within the reaction slurry generates heat that is used to heat the reaction slurry. As such, there is less need for additional process heating.
- the recovery of ammonia by way of the present invention may be further heightened through the further boiling of the air or steam stripped discharge slurry or filtrate produced from the reaction slurry.
- a feed solution of ammonium sulphate was fed with quicklime to a vertical stirred mill with alumina balls and having compressed air injected from the bottom of the mill and bubbled through the slurry. This "wet milling" was conducted over a period of 120 minutes at ambient temperatures, the temperature being recorded as below:
- NH 3 -N% refers to the percentage of nitrogen in each of the ammonium sulphate, residue and solution present as NH 3 .
- Mass NH 3 -N(g) refers to the mass (in grams) of nitrogen present in each of the noted groups, as NH 3 .
- NH 3 -N Gas (%) refers to the percentage of gaseous nitrogen present as NH 3 .
- Example 3 This process was conducted in the same manner as that of Example 1 other than additionally boiling the residue filtrate from the ball mill for 30 minutes to strip ammonia. This additional boil step strips off most remaining ammonia and produces a still higher level of ammonia recovery, as may be seen with reference to Table 1.
- Example 3
- a vibrating drum grinding mill was modified to become the reactor for this example.
- This reactor is a horizontal non-rotary mill which combines drum like rotary particle motion with constant, aggressive high frequency particle agitation to achieve size reduction.
- the mill was charged to 40% by volume with steel grinding media, together with 12 L of 150g/L ammonium sulphate solution. Quicklime was added directly to the mill. Air or steam (as required) were injected into the slurry inside the mill as it operated to strip the ammonia from the solution.
- Example 3 The test of Example 3 was run at ambient temperature with no air or steam stripping. Upon adding quicklime, ammonia evolution started immediately, and the mill became hot due to the reaction heat of lime slaking. Ammonia gas continued to be emitted from the mill after 4 hours of milling.
- the heat generated by the slaking of the lime is used to heat the reaction slurry. Further, as no extra water is added, in the form of milk of lime which would act to dilute the ammonia concentration in the reaction slurry, a more concentrated ammonia product solution may be obtained, whilst also leading to lower steam consumption.
- the milling action employed in the process of the present invention both provides high utilisation of quicklime through the continual abrading of the gypsum surface of the particles, and substantially prevents fouling of the reaction vessel and other equipment by gypsum precipitates.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA01007088A MXPA01007088A (en) | 1999-01-12 | 2000-01-12 | Ammonia recovery. |
CA002359930A CA2359930A1 (en) | 1999-01-12 | 2000-01-12 | Ammonia recovery |
AU24241/00A AU765545B2 (en) | 1999-01-12 | 2000-01-12 | Ammonia recovery |
EP00902491A EP1165439A1 (en) | 1999-01-12 | 2000-01-12 | Ammonia recovery |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPP8158A AUPP815899A0 (en) | 1999-01-12 | 1999-01-12 | Ammonia recovery |
AUPP8158 | 1999-01-12 | ||
AUPQ0314A AUPQ031499A0 (en) | 1999-05-12 | 1999-05-12 | Ammonia recovery |
AUPQ0314 | 1999-05-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000041967A1 true WO2000041967A1 (en) | 2000-07-20 |
Family
ID=25645972
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU2000/000014 WO2000041967A1 (en) | 1999-01-12 | 2000-01-12 | Ammonia recovery |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1165439A1 (en) |
CA (1) | CA2359930A1 (en) |
MX (1) | MXPA01007088A (en) |
WO (1) | WO2000041967A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005097680A1 (en) * | 2004-04-07 | 2005-10-20 | Western Minerals Technology Pty Ltd | Process for the regeneration and recovery of ammonia |
AU2005231516B2 (en) * | 2004-04-07 | 2010-03-11 | Mpi Nickel Pty Ltd | Process for the regeneration and recovery of ammonia |
CN102167353A (en) * | 2010-12-22 | 2011-08-31 | 浙江海虹控股集团有限公司 | Reaction device with internal material returning function for recycling ammonia by dry method |
WO2013116903A1 (en) | 2012-02-10 | 2013-08-15 | Phylogica Limited | Methods for the characterisation of interaction sites on target proteins |
WO2014188077A1 (en) | 2013-05-23 | 2014-11-27 | Outotec (Finland) Oy | Method for recovering metals |
DE102014212827A1 (en) * | 2014-07-02 | 2016-01-07 | TIEBECK GmbH & Co. KG | Method and device for mechanical ammonia stripping in a biogas plant - "Mechanical stripping" |
CN114405962A (en) * | 2021-12-28 | 2022-04-29 | 武汉大学(肇庆)资源与环境技术研究院 | Method for efficiently removing ammonia nitrogen in electrolytic manganese slag |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102167354B (en) * | 2010-12-22 | 2013-02-06 | 浙江海虹控股集团有限公司 | Reaction device for recovering ammonia with dry method |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4045341A (en) * | 1976-01-22 | 1977-08-30 | Nittetu Chemical Engineering Ltd. | Method for the disposal of waste water containing ammonium ions, sulfate ions and organic substances |
JPS539050A (en) * | 1976-07-13 | 1978-01-27 | Mitsui Constr | Treating method of ammonia containing drainage |
US4294812A (en) * | 1978-05-25 | 1981-10-13 | General Electric Company | Recovery of ammonia from aqueous streams |
DD157253A1 (en) * | 1981-03-18 | 1982-10-27 | Hans Hofmann | METHOD FOR PRODUCING A CALCIUM CARRIER PARTICULARLY SUITED FOR GLASS MANUFACTURE |
US4394363A (en) * | 1979-01-29 | 1983-07-19 | Dr. C. Otto & Comp. G.M.B.H. | Process for the granulation of precipitation products formed from ammonium compounds |
JPS6246919A (en) * | 1985-08-26 | 1987-02-28 | Nippon Kokan Kk <Nkk> | Method for recovering nh3 from aqueous ammonium sulfate solution |
-
2000
- 2000-01-12 MX MXPA01007088A patent/MXPA01007088A/en unknown
- 2000-01-12 WO PCT/AU2000/000014 patent/WO2000041967A1/en not_active Application Discontinuation
- 2000-01-12 EP EP00902491A patent/EP1165439A1/en not_active Withdrawn
- 2000-01-12 CA CA002359930A patent/CA2359930A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4045341A (en) * | 1976-01-22 | 1977-08-30 | Nittetu Chemical Engineering Ltd. | Method for the disposal of waste water containing ammonium ions, sulfate ions and organic substances |
JPS539050A (en) * | 1976-07-13 | 1978-01-27 | Mitsui Constr | Treating method of ammonia containing drainage |
US4294812A (en) * | 1978-05-25 | 1981-10-13 | General Electric Company | Recovery of ammonia from aqueous streams |
US4394363A (en) * | 1979-01-29 | 1983-07-19 | Dr. C. Otto & Comp. G.M.B.H. | Process for the granulation of precipitation products formed from ammonium compounds |
DD157253A1 (en) * | 1981-03-18 | 1982-10-27 | Hans Hofmann | METHOD FOR PRODUCING A CALCIUM CARRIER PARTICULARLY SUITED FOR GLASS MANUFACTURE |
JPS6246919A (en) * | 1985-08-26 | 1987-02-28 | Nippon Kokan Kk <Nkk> | Method for recovering nh3 from aqueous ammonium sulfate solution |
Non-Patent Citations (3)
Title |
---|
DATABASE WPI Week 197810, Derwent World Patents Index; Class D15, AN 1978-18671A * |
DATABASE WPI Week 198310, Derwent World Patents Index; Class L01, AN 1983-22696K * |
PATENT ABSTRACTS OF JAPAN * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005097680A1 (en) * | 2004-04-07 | 2005-10-20 | Western Minerals Technology Pty Ltd | Process for the regeneration and recovery of ammonia |
AU2005231516B2 (en) * | 2004-04-07 | 2010-03-11 | Mpi Nickel Pty Ltd | Process for the regeneration and recovery of ammonia |
CN102167353A (en) * | 2010-12-22 | 2011-08-31 | 浙江海虹控股集团有限公司 | Reaction device with internal material returning function for recycling ammonia by dry method |
CN102167353B (en) * | 2010-12-22 | 2012-09-05 | 浙江海虹控股集团有限公司 | Reaction device with internal material returning function for recycling ammonia by dry method |
WO2013116903A1 (en) | 2012-02-10 | 2013-08-15 | Phylogica Limited | Methods for the characterisation of interaction sites on target proteins |
WO2014188077A1 (en) | 2013-05-23 | 2014-11-27 | Outotec (Finland) Oy | Method for recovering metals |
US10174400B2 (en) | 2013-05-23 | 2019-01-08 | Outotec (Finland) Oy | Method for recovering metals |
DE102014212827A1 (en) * | 2014-07-02 | 2016-01-07 | TIEBECK GmbH & Co. KG | Method and device for mechanical ammonia stripping in a biogas plant - "Mechanical stripping" |
CN114405962A (en) * | 2021-12-28 | 2022-04-29 | 武汉大学(肇庆)资源与环境技术研究院 | Method for efficiently removing ammonia nitrogen in electrolytic manganese slag |
Also Published As
Publication number | Publication date |
---|---|
MXPA01007088A (en) | 2003-07-21 |
EP1165439A1 (en) | 2002-01-02 |
CA2359930A1 (en) | 2000-07-20 |
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