WO1995032152A1 - Method for purifying impure aluminium oxide by extraction - Google Patents
Method for purifying impure aluminium oxide by extraction Download PDFInfo
- Publication number
- WO1995032152A1 WO1995032152A1 PCT/FI1995/000272 FI9500272W WO9532152A1 WO 1995032152 A1 WO1995032152 A1 WO 1995032152A1 FI 9500272 W FI9500272 W FI 9500272W WO 9532152 A1 WO9532152 A1 WO 9532152A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organic
- aluminium oxide
- impure
- solvent
- dissolving
- Prior art date
Links
Classifications
-
- 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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
Definitions
- the invention relates to a method for purifying impure aluminium oxide and to the use of aluminium salts produced with this method as a raw material in industrial applications.
- aluminium oxide is used to regenerate and remove organic secondary products formed in the working solution.
- the porosity of active aliiminium oxide allows it to be used particularly in the anthraquinone process with a view to adsorb spent organic compounds.
- the impurities are mostly aromatic hydrocarbons.
- aluminium oxide is removed from the process and replaced with a new oxide.
- Spent aluminium oxide contains organic substances which restrict its utilisations. At present, residual aluminium oxide is usually disposed of as a waste, or optionally stored for the eventuality of ultimate utilisation.
- US patent specification 3 814 701 sets out removal of orgamc matter from spent alumimum oxide deriving from an anthraquinone working solution by calcinating sduminium oxide at a temperature of 300-400 °C.
- the organic matter adsorbed into aluminium oxide will be removed by combustion during calcination.
- the calcinated alumimum oxide is then subjected to caustic treatment and recalculation. Nonetheless, treated in this way, aluminium oxide is highly dusting if recycled in the H2O2 process.
- DE patent application 4 027 159 describes purifying impure aluminium oxide with a method comprising dissolving aluminium oxide into mineral acids or lye.
- the component insoluble in acids or lye is separated, the purified aluminium oxide is filtered, dried and eventually calcinated.
- the patent application does not specify how the various steps of the invention can be perforaied. All the same, the aluminium oxide dissolved in acids or lye and the accompanying impurities constitute a diphase solution which is particularly hard to treat, containing a tar-like, sticky organic phase. Technically speaking, it is nearly impossible to perform additional treatments of great volumes of such a solution.
- the purpose of the present invention is to provide a method for removing organic substances from aluminium oxide waste deriving from the hydrogen peroxide process.
- the goal of the method of the invention is to allow controlled, safe and environment-friendly purification of contaminated and impure alumimum oxide, allowing the alumimum salts obtained as a product to be used as a raw material in industrial applications.
- Another goal of the method of the invention is to avoid the calcination step, which is most expensive.
- a further goal is not only to recycle the organic compounds forming impurities but also to utilise them as a fuel.
- the invention relates to a new method for purifying impure aluminium oxide, which has been used in hydrogen peroxide preparation for the adsorption of organic components.
- the method of the invention makes it possible to obtain a perfectly pure aluminium salt, such as aluminium sulphate or aluminium chloride, which is even purer than commercially available products.
- aluminium salts prepared with this method are well suited to be used as raw materials in industrial applications, particularly the alruninium salts are suitable to be employed as water purification and retention chemicals.
- organic hydrocarbons present as impurities in Eduminium oxide are recovered into the solvent and can be recycled to the extraction step, and part of them can be utilised as a fuel.
- part of the organic hydrocarbons can be dissolved into the solvent in prepurif ⁇ cation, and its useful components can be recycled in the hydrogen peroxide process.
- Porous, active aluminium oxide is used to regenerate the working solution in the preparation of hydrogen peroxide with the anthraquinone method.
- Porous aluminium oxide adsorbs mainly the organic hydrocarbons used as an anthraquinone solvent, working solution components and other degradation and oxidation products from the working solution.
- solvents for anthraquinone working solutions we cite among others secondary alcohols, trialkyl phosphates, alkyl benzenes, triacetyl benzene, alkyl cyclohexanones, naphtalenes, xylenes, anilines and quinones.
- the working solution may further contain many other substances used to dissolve anthraquinone.
- the inactive and impure aluminium oxide removed from the process may thus contain different organic matters in varying amounts, depending on the hydrogen peroxide manufacturing process.
- the impure aluminium oxide can be prewashed with an organic hydrocarbon solvent before thermal treatment.
- the washing solvent may consist of any organic hydrocarbon capable of dissolving the organic component forming an impurity in aluminium oxide.
- a preferred embodiment uses Shellsol AB as a solvent, which is a commercially available product containing mainly CJO-CI J aromatic hydrocarbons. Prewashing allows those organic useful components to be extracted from aliiminium oxide which are recyclable directly to the hydrogen peroxide process. Moreover, prewashing allows the amount of burnt organic matter to be reduced and simultaneously the organic compounds to be recirculated in the hydrogen peroxide process.
- the invention recommends pulverisation of the impure aluminium oxide. In fact, it was found that the finer the a___minium oxide, the more complete was the acid dissolving. It is advisable to grind aluminium oxide to a particle size 100% under 0.5 mm, preferably 100% under 0.4 mm.
- the acid dissolving-extraction step comprises dissolving ground _d__minium oxide in a concentrated acid solution. Any concentrated mineral acid is appropriate for dissolving, however, sulphuric and hydrochloric acid are recommended. Sulphuric acid used in a 50-60% by weight concentration is considered particularly suitable.
- the dissolving is appropriately enhanced by heating. To ensure nearly complete dissolving of aluminium oxide it is recommended to heat the mixture to a temperature of about 100-160 °C, while stirring for several hours. In the course of dissolving, the organic component contained in aluminium oxide is separated into a separate phase on the surface of the aqueous phase. The reaction mixture is diluted with water to prevent aluminium salts from crystallising. Separation of organic components is enhanced by extracting by means of either entirely pure or entirely recycled, or partly recycled and partly pure organic solvent.
- the extraction solvent may consist of any organic hydrocarbon capable of dissolving organic components from aluminium oxide.
- a preferred embodiment uses Shellsol AB as a solvent, which is a commercially available product containing mainly Cjo-Cn aromatic hydrocarbons.
- Toluene is a particularly advantageous solvent, which after the phase separation can be easily distillated from the organic phase and returned to the step following dissolution.
- the recycled organic solvent to be returned to the extraction step can, if desired, be purified after the phase separation, and if necessary, enhanced with a pure solvent.
- the phases are allowed to separate. Impurities in the organic phase settled on the surface mainly contain organic components deriving from the apatinium oxide and possibly also organic solvents used in extraction.
- the organic phase is partly returned to the extraction step and partly conducted to a combustion plant. If desired, the portion returned to the extraction step can be purified, for instance by distillation.
- the aqueous phase settled on the bottom is filtered to remove undissolved components.
- the precipitate is returned to the dissolving step, burnt along with organic components, or collected as waste.
- the filtrate, containing aluminium salt is usable as such as an aqueous solution or can be solidified by crystallising.
- the aqueous phase is repurified after filtering in order to remove organic residues that may remain in the aqueous phase.
- Purification can be performed with an active carbon treatment.
- Other chemicals may also be used, for instance flocculating agents, instead of or along with active carbon.
- the perfectly pure aqueous solution of aluminium salt can be used as such, or supplied in a solid crystallised form for use say, as a water purification or retention chemical.
- FIG. 1 shows a block diagram of the various steps of the invention.
- impure aluminium oxide is ground and subsequently dissolved in an acid.
- Organic impurities are separated as an organic phase.
- the mixture is diluted with water, and the separation of organic impurities is enhanced with extraction by using recycled and/or pure organic solvents.
- After the phase separation a portion of the organic phase is conducted to a combustion plant and another portion is recycled to the extraction step.
- the aqueous phase is filtered or centrifugated. Undissolved components from the aquoeus phase are returned to the dissolving step and the filtrate is used as such or is further purified.
- Impure aluminium oxide supplied by a hydrogen peroxide plant was ground to a particle size under 0.35 mm.
- a Schwing mill was used for grinding and a screen was used to obtain the particle size desired.
- Table 1 sets out the dissolution yield in sulphuric acid obtained in three tests. Aluminium oxide was dissolved in the same way in all of the three tests. Sulphuric acid was introduced in water (164 g) in a flask, causing the temperature to rise to approx. 70 °C. Aluminium oxide (100 g) was gradually added to the mixture of water and sulphuric acid. During the adding no visible reaction occured, nor did the temperature rise owing to the added alumimum oxide, but the flask had to be continuously heated to prevent a drop of temperature. Eventually the temperature was raised to 90-110 °C. The mixture was maintained at the boiling point for 3 h. Its colour was dark brown. The mixture obtained was diluted with water. The goal was to obtain an 8% solution with regard to aluminium oxide.
- the extraction solution was introduced in a 2 1. flask containing the diluted A_2 (S ⁇ 4)3 solution (table 2), and when using toluene the temperature was allowed to drop below 50 °C before adding the solution in order to prevent evaporation. Stirring was continued for 1 h.
- the extraction solution in test 3 consisted of distillated toluene from test 2 and "fresh" toluene to compensate for the solution loss in test 2 (table 2).
- a brown “ring” of organic component sticked to the flask sides, which did not dissolve directly under stirring in the extraction solution, but had to be "scaled off 1 , and thus it was indeed dissolved.
- Toluene (99.1 g) was distillated in a round-bottomed flask, which was heated to 111 °C. The temperature eventually rose to 116 °C, and at that point the distillation was interrupted. There was a yield of 78.1 g of distillate, which was a clear, colourless liquid. There was 17.9 g of brown distillation residue. The distillation loss was 3.1%.
- the insoluble precipitate was separated from the aqueous phase deriving from the extraction step either by filtering or by centrifugating.
- Test 1 related to separating the precipitate by filtering.
- a 0.1% solution of a flocculating agent i.e. 12 ml of Fennopol K 211 was added at a ratio of 30 ppm to about half of the aqueous phase obtained, i.e. 400.9 g. Agitation by means of a Heidolph mixer for 15 sec, speed of rotation 450 rpm.
- the Fennopol addition yielded an easily settling floe.
- the mixture obtained was filtered with a Buhner device with a diametre of 9 cm.
- a glass fibre paper, Whatman GF/A, was used. Vacuum was sucked with a vacuum pump, under a pressure of 600 mbar. The filtrate obtained was taken apart and the precipitate was washed with warm water (table 4). The precipitate was dried in a heating chamber at 100 °C overnight.
- test 1 The amount of sulphuric acid used to dissolve aluminium oxide (test 1 : stoichiometric amount and test 3: 95% of the stoichiometric amount) did not affect akrminium and iron solubility. In both the tests 90% of alumimum and 98.4% of iron was dissolved in the aqueous phase (table 5).
- the active carbon treatment of the water phase dropped the turbidity to the range of 0.15 to 0.5 and the TOC to the range of 0.004 to 0.006% (table 4).
- test Aqueous phase Filtrate Insoluble No Wash treatment amount sample amount P pH pH turbidity TOC Fe % Al water sample g % Fe % Al g No g g/cm 1 :10 % % g No % 3
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Extraction Or Liquid Replacement (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7530075A JPH10500931A (en) | 1994-05-20 | 1995-05-19 | Purification method of impure aluminum oxide by extraction |
EP95918629A EP0796224A1 (en) | 1994-05-20 | 1995-05-19 | Method for purifying impure aluminium oxide by extraction |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI942338A FI98508C (en) | 1994-05-20 | 1994-05-20 | Method for purification of impure alumina by extraction |
FI942338 | 1994-05-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995032152A1 true WO1995032152A1 (en) | 1995-11-30 |
Family
ID=8540737
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FI1995/000272 WO1995032152A1 (en) | 1994-05-20 | 1995-05-19 | Method for purifying impure aluminium oxide by extraction |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0796224A1 (en) |
JP (1) | JPH10500931A (en) |
FI (1) | FI98508C (en) |
WO (1) | WO1995032152A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0801029A1 (en) * | 1996-04-12 | 1997-10-15 | Kemira Chemicals Oy | Method for the treatment of impure aluminium oxide |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105836865B (en) * | 2016-06-04 | 2018-05-15 | 江阴市长江化工有限公司 | A kind of preparation process of aluminium polychloride |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4027159A1 (en) * | 1990-08-28 | 1992-03-05 | Niermann Hermann Dr | Alumina recovery esp. from hydrogen peroxide mfr. by autoxidation - by heating in aq. liq., sepg. solid impurities, filtering, drying and calcining |
SE500108C2 (en) * | 1988-05-27 | 1994-04-18 | Nokia Oy Ab | Less basic aluminum hydroxychloride, methods of preparation and use thereof |
-
1994
- 1994-05-20 FI FI942338A patent/FI98508C/en active
-
1995
- 1995-05-19 JP JP7530075A patent/JPH10500931A/en active Pending
- 1995-05-19 WO PCT/FI1995/000272 patent/WO1995032152A1/en not_active Application Discontinuation
- 1995-05-19 EP EP95918629A patent/EP0796224A1/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE500108C2 (en) * | 1988-05-27 | 1994-04-18 | Nokia Oy Ab | Less basic aluminum hydroxychloride, methods of preparation and use thereof |
DE4027159A1 (en) * | 1990-08-28 | 1992-03-05 | Niermann Hermann Dr | Alumina recovery esp. from hydrogen peroxide mfr. by autoxidation - by heating in aq. liq., sepg. solid impurities, filtering, drying and calcining |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0801029A1 (en) * | 1996-04-12 | 1997-10-15 | Kemira Chemicals Oy | Method for the treatment of impure aluminium oxide |
US5942199A (en) * | 1996-04-12 | 1999-08-24 | Kemira Chemicals Oy | Method for the treatment of impure aluminium oxide |
Also Published As
Publication number | Publication date |
---|---|
FI942338A0 (en) | 1994-05-20 |
EP0796224A1 (en) | 1997-09-24 |
FI98508B (en) | 1997-03-27 |
JPH10500931A (en) | 1998-01-27 |
FI942338A (en) | 1995-11-21 |
FI98508C (en) | 1997-07-10 |
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