2) United States Patent Tizon et al. (54) BAYER PROCESS FOR PRODUCTION OF ALUMINA TRINYDRATE BY ALKALINI DIGESTION OF BAUXITE, THE PROCESS COMPRISING A PREDESILICATION STEP Inventors Eric Tizon, Aix en Provence (FR) Clotilde Fryns, Aix en Provence (FR) Assignee: Aluminium Pechiney (FR) Notice: Subject to any disclaimer, the team ofthis, patent is extended or adjusted under 35 USC. 154(b) by 406 days, ay Appl.Nos —11569,290 (22) PCT Filed: May 11,2005 (86) PCTNo: — PETIFR200S/001177 $371 (00), (2),(4) Date: Now. 17, 2006 (87) PCT Pub, No WO2008/123591 PCT Pub. Date: Dee. 29, 2005 ws) Prior Publication Data $ 200710178041 AL Aug. 2, 2007 G0) May 18, 2004 Fore (eR) Application Priority Data 04 05405, (1) Ince (2006.01) 2) 68) azsni21; 423/625 424/121, 14231625 ‘See pplication ile for complete search history. References Cited (56) US. PATENT DOCUMENTS 2AIROST A 1/1968 Roberts ‘US0O7704471B2 US 7,704,471 B2 Apr. 27, 2010 (10) Patent No. 4s) Date of Patent: 3ABI,705 A 121969 Pocket BSSR53S A 121974 Suabo Noe Mogyoros ca. 4289629 89/1981 Anizew 4426363 VISE Yamada A010 8 21981 Malt eta FOREIGN PATENT DOCUMENTS 44506 B 9822300 A rom wo S198 * cited by examiner Primary Bxaminer—Steven Bos 74) Attorney Agent, or Firm Banner & Witeoll, Lid on ABSTRACT A Bayer process comprises prinding and then digestion of ‘bauxite by bringing it into contact with a sodium aluminate liquor, Digestion consists of forming a slurry that is then treated to separate insoluble resides from the sodium slumi- rate liquor. The liquors then crystallized and recycled back to green liquor after having been separated from the alumina teihydrate precipitated during crystallization. The process ‘comprises predesilication treatment during which the round bauxite, before digestion, is brought into contact with fan aqueous sodie solution that has a content of earbonstes, ‘lpates and possibly chlorides Which, expressed a8 per centage related to thecaustic concentration, has less than half of the coresponding impurities eontent of the spent liquor. Proforably, the pure caustic soda used to compensate for ‘caustic soda Tostes in the Bayer cect, previously injected jst aller evepornion, is now added in the aqueous sodic solution for the predesiication treatment 5 Claims, 4 Drawing SheetsU.S. Patent ‘Apr. 27, 2010 Sheet 1 of 4 US 7,704,471 B2U.S. Patent ‘Apr. 27, 2010 Sheet 2 of 4 US 7,704,471 B2 14U.S. Patent ‘Apr. 27, 2010 Sheet 3 of 4 US 7,704,471 B2U.S. Patent ‘Apr. 27, 2010 Sheet 4 of 4 US 7,704,471 B2US 7,704,471 B2 1 BAYER PROCESS FOR PRODUCTION OF ALUMINA TRIHYDRATE BY ALKALINE DIGESTION OF BAUNITE, THE PROCESS. COMPRISING A PREDESILICATION STEP. (CROSS REFERENCE TO RELATED "APPLICATIONS, Tis application claims the benefit of priority ofthe filing date of Patent Cooperation Treaty patent application, Serial ‘Nuzubee PCT/FR2005/00117, filed on May 11, 2005, whieh js incorporated herein by ference, wherein Patent Coopers- tion Treaty patent application Serial Number PCT/FR200S) OOL177 as not published under PCT Anicle 21(2) in English, and also claims the benefit of prcrty ofthe filing date of French patent application, Application No. FR (0405405, fled on May 18, 2004, which incorporated herein by reference FIELD OF THE INVENTION ‘The invention relates to a process for the production of ‘alumina tibydrate by alkaline digestion of bauxite using the Bayer process, comprising grinding and then digestion ofthe ground bauxite by bringing it into contaet with a sodium > aluminate Tiquor (green liquor, the digestion consisting of orming a shar that steated to separate insoluble resiciues from the sodium aluminate liguoe, the aluminate liguor thus ‘obtained then being crystallized and recycled back to green liquor after being separated from the lumina trihydrate pre- tated during the crystallization. More particulary, dhe invention relates toa process forreducing the content of silica dissolved in the aluminate liquor circulating in the Bayer cient, BACKGROUND ‘he content of slic dissolved in the aluminate liquor must be controlled to prevent sealing of pipes in the Bayer circuit and fo control the purty of the tihydrate produced. The Vigilance necessary for this contol varies depending on the nature of the treated beuxite, Paradoxically, this control is ‘most difficult for bauxites with a low content of reactive silica. Afirstypeof dasilication seared outon the entire liguor itself For example, it is eartied out immediately aller diges- tion with sufficiently long residence time forthe quantity of dissolved silica to reich a eal supersaturation threshold, ‘which triggers the desiicaton reaction by precipitation of siliceous compounds and leads to a deop in the eoncentraton ‘of silica in the liquor to an acceptable level jast before sepa ration of the insoluble residues. It can also be carried out before digestion, by locally introducing precipitation germs: Jor example, inthe process described By U.S. Pat, No, 6.086, 834 (ALCAN), in which the liquor must passthrough a bed ‘composed of @ mix of sand and sodalite, or in the process ‘described in French application No, 03 11909 (ALU- MINIUM PECHINEY) in which a caleium based compound (ypically comprising hydrogaracts) is introduced into the aluminate Hiquor upstream of the heat exchangers ‘A second type of desilication is called “predesfication” bocatse the ground bauxite is brought into contact with an alkaline solution before digestion. U.S. Pat, No. 3,481,705, AU Patent No. 0474 $96 and US. Pat. No. 4,426,368 “describe a predesilication treatment, where the alkaline solu tion may’ Be sodium hydroxide soktion, optionally mixed with sodium carbonate, a potassium hydroxide solution or, o 2 preferably, a Bayer aluminate liquor. Using the latter is pre- {ered becinne it is not expensive: a small part of the Bayer spent liquor s drawn off nd conducted tothe wet grinding of the bauxite. The thick slurry resulting from wet grinding is ‘maintained ina tank typically a few hours before digestion. ‘The silica contained in the bauxite is dissolved in this liquor Aliquot, which quickly reaches a supersaturation threshold from which the precipitation of desiliation products (DSP) ‘occurs. The DSP are then eliminated with the insoluble re ‘dues bauxite digestion Predesilication also acts directly on ‘bauxite components added into the Buyer circuit, but unlike the fist ype of treatments, it cannot be used efliiently 10 reduce the silica content of the liquor quickly ata precise location of the Bayer eieuit. For this reason, both types of esiicaion treatments are generally combined on the same ayer process. This invention relates to an improvement to the predesi cation treatment, The predeslication treatment may he con- sidered as being a preventive treatment carried out on the ‘buuxite thats introduced into the Bayer circuit. However, this {ype of treatment ean only be ficient ft prevents the liquor {rom reaching a given critical concentration threshold of di solved siliea before erystallization —typically a ilica/caustic soda ratio oF ahout 0.7% for factories with a caustic soda concentration of about 185 / (note in the following that such ratios ae referenced tthe Weight of east soda "26 tg", oF in fact" SiO, e1g")s0 that in particular the purity ofthe ‘einydrate produced can be controlled. Ts found tha predesieaion treatments recommended by ferent documents according to prior art are often appar- cll efficient, but cannot always achieve a suficiently low ‘eantent of dissolved silica inthe liquor. "A perfect predesilication would consist of transforming all soluble siliceous phases of bauxite (Tor example Kaolinite) into the most stable possible phase (DSP) under digestion conditions. In this way, the concentration of silica in the Tiquor t the output from digestion would be less than or ‘equivalent to the DSP solubility concentration (solubility between 0.5 and 0.9% ctq depending om digestion cond tions), However, inthe article “Feet of Predesiication and Digestion Conditions on Silica Level in Bayer Liguoe’— Light Metals 2004 TMS, 2004, the ators (E, TIZON, Ph CLERIN, B. CRISTOL} demonstrated that the supposedly insoluble phases (DSP) erated during predesilieation are not all stable under digestion conditions, particularly for re ‘dence times typically used in te indusry (6 t0 10h), and that theie dissolution during the digestion may finally partieipate in the increase in the content o silica dissolved in the liquor ‘Thus, under some conditions in predesilicaionasitis carried ‘out in the prior art, the silica content dissolved in the alumi fate liquor downstream of digestion canaot be ellcictly controled Tt has also been demonstrated that solubility of DSP ‘increases greatly when the concentration of alumina increases. Thus, this loss of efficiency of predesiication may ‘in particular lead to production losses daring digestion (the lumina concentration is Timed by the sliea concentration). SUMMARY OF THE INVENTION Therefore, in order to increase the efficiency of predesi cation, the applicant looked fora process to reduce the solu- bility ofthe DSP formed while enabling eesimum transfor ‘mation of soluble siliceous phases into DSP. ‘A fist purpose of the invention iso provide a process for production of alumina talaydrate by alkaline digestion of bauxite using the Bayer process, comprising grinding andUS 7,704,471 B2 3 then digestion ofthe sound bauxite by bringing it into tact with a sodium aluminate liquor (greca liquor), the diges- tion consisting of forming a slurry tht is then treated 0 separate insoluble residues of sodium aluminate Figuor, the aliminate liquor ths obtained then being crystallized and recycled ack tothe groen liquor after having heen separated from the alumina trihydrate precipitated during the crystal zation step (and generally concentrated by evaporation), the Bayer process comprising predesilcaton treatment during which the ground bauxite is brought into contact with aa ‘aqueous soe solution before digestion, wherein theaqueous ‘ic solution that i used forthe predesiiation treatment is atleast parially drawn off from the Bayer line and is treated jnsuch a manner thatit has caustic concentration of beeen 60g NaOlliter and 220 g Na, Ovlter anda weight content of ‘carbonates and sulphates or sulphites, which, whenexpressed 288 a percentage related to the caustic concentration, is less than half the corresponding impurities weight content ofthe spent liquor FIGURES FIG. 1 illwsirates the dissoluion mutes of silica durin «digestion with sodalitessynthesizedunder different peedes ‘ation conditions, namely using an aqueous sodie solution ‘containing more or less impurities. TIG. 2showsa diagram of the steps ofa particular embod ment of the process according fo the invention, used within the context of improved digestion wih sweetening described in EP 0.960 069. FIG, illustrates three silica dissolution rates during diges- tion with sweetening as shown in FIG. 2, each of these curves relating to the use of a particular aqueous sodie solution mended for predestiation of gibbsite FIG. 4 showsa diagram of the steps of particular embod meat ofthe process according tothe invention, temporarily used within the context of a “conventional” Bayer process. DETAILED DESCRIPTION OF EMBODIMENTS (OF THE INVENTION ‘The weight content of carbonates and sulphites or sul: phates is expressed independently ofthe associated cations. For example the content of carbonates can be express i termi ofthe weight of CO, per uit volume. We will denote this percentage as “% CO, elg” when itis expressed as @ Percentage related to the equivalent caustic concentration, ‘self expressed s the Weight of Na,O per unit volume. Si ‘thecontent of sulphites or sulphates can be expressed in terms of the weight of the SO, per unit volume. We will denote this percentage as "% SO, cfg” when itis expressed as ‘a percentage relate to the equivalent caustic concentration, ‘Concentrations of earbonate and sulphate or sulphite impu- js in Bayer liquors depend on the nature ofthe digested hauxtes, and for this reason we cannot define eritcal con- ‘entrations of impurities by absolute values. The important thing here is to avoid the presence ofthese impurities, or at least to significantly reduce their quantity, inthe step in the [ayer circuit at which they could be most harmful Typically, ora Bayer circuit witha spent liquor containing 12%CO, ctq and 2% SO, etg, the concentration of carbonates inthe aque- ‘ous sodie solution use for predesilication must be les than 6% CO, etq, and the corresponding concentration in sul- phates o sulpites must be less than 1% SO, et By carailly observing the many precipitated produess appearing during a predesilication treatment, the applicant surprisingly observed that among the DSPs obtained, no all 0 o 4 ‘compounds belonging tothe sodalite family are as stable as suggested in the specialized literature. In particular he ‘observed that sodalites ae more stable in digestion i they ‘contain fewer carbonate, sulphate or sulphite ype fons, and ‘more aluminate ions. The sodalites formed are represented by the following general Formul Ni, 0250,41,0,40N4%) where ¥ represents CO? one ‘One mote of silica corresponds to one sixth of a mole of 1Na.Y, which behaves like a “cage” tupping one carbone, sulphate or sulphite fon, or two chloride or aluminate ions. The applicaat observethat the stability of sodalites during digestion cond depend strongly of the nature of the Hons ‘originating fom the aqueous solution used for treatment of predesiicaton and tapped by Na, cages. Sodalitesinclud- ng aluminate ions aze the most siable, Sodalites containing carbonate fons andor sulphate of sulphite ions are the last Sable, To a lessee extent, chloride ions alsa have a negative influence on the stability of sodalite during digestion, One preferred embodiment of the invention consists of ‘using an aqueons sodic solution For predesiieation for which the chloride weight content i also Tess than a half of the chloride weight content of the spent liquor. The chloride ‘Weight content may be expressed in terms of weightof Cl per ‘unit volume. We will denote this percentage as "% Cl et when it is expressed a a pereentage related tothe equiva caustic concentration. Typically, for a Bayer circuit with spentliquor containing 4% Cletg, theehloride weight content inthe aqueous soe solution use for predesliation must be less than 2% Cl eg. Te Bayer aluminate liguor hasan almost dential content of impurities (% SO, ct, % CO, ct ar % Cl ea) regardless ‘ofthe pont at which it has been drawn off (before digestion, aller digestion or aftr dilution). Variations of these contents ‘overtime may be du toa change inthe bauxite quality (the ‘main entry of impurities inthe cycle) or toa modification of soluble caustic soa losses (the main cause of impurity losses inthe eyele). Weekly monitoring i often sufficient to record ‘change in these impurity contents, which vary only slightly ‘with Gime in any one given factory, ‘Until no, the aqueous soi solution nsed for predesiia- ‘ion was traditionally an aliquot of the spent aluminate liquor According to the present invention, the aqueous sodic soht- tion is atleast partially raven of from the Bayer Hine nd is ‘weated in such a manner that it contains less impurities, such assulphites and/or sulphates, carbonates and optionally chlo- ‘ides, than the aluminate liquor tht flows through the Bayer Tine. It may be an aliquot of spent liquor that should be purified in order to contain fewer impurities. [¢may also bea ayer elflient that has a lower caustic coneeatration, 19 cally a washer overflow, which should be teated, for example by adding sodium hydroxide in order to have a caustic eon- centration between 60 g Na,Oiliter and 220 g Na,Oliter the aqueous sodic solution used forthe predeslication is ‘an aliquot ofthe pregnant liquor, most oral of its impurities, {ypically carbonate, sulpaste or slphite tons, are climsinated ing. a specific purification treatment such as membrane filtration or precipitation ‘The aqueous sodic solution used for the predesiliation ‘may also result from a mix of pare agucos sodium hyrox- ‘de solution wth aluminate Hiquor drawn ofT ata point inthe [ayer circit at which it has the lowest possible impurities content. The aqueous sodium hydroxide solution ean be +80, or 80, or 201 or 2AUS 7,704,471 B2 5 ‘obtained by diluting trade sodium hydroxide (hereinateralso called“ pure caustic sada” or“new caustic soda”) water hat has controlled impurities conten. Ideally, this water may be derived from condensates derived from evaporation of water ‘nthe evaporation or digestion steps; it may also be hot water ‘utp fiom purging plant hoilers or raw water. This alumi nate lquor, typically the caustifietion seting tank overflow fr the first washer overflow, oF any other washer overflow from hydrate washer series, hs a eausti soda concentration ‘of 30 to 60 gi. The impurity level expressed as % ct is ‘dentcal for most ofthese liquors, but they have the advan- tage that they also havea lower concentration ofeaustie soda (iypically 30-70 1 insted of 160-180 g/) than the spent Tiguor, so thatthe global quantity of impurities input in pre- aluminate liguor, wherein the digestion comprises forming 2 slurry that includes the ground bauxite, the aqueous sodic solution and the sodium aluminate liquor and tenting the slurry to separate insoluble residues from the sodium alumi nate liquor. and wherein the resulting portion of the slurry without insoluble residues is defined asa “preynant Hiquor", (4) crystallizing the pregnant liquor whereby alumina triy= “dates precipitated and where the sodium aluminate ighor 12 without the precipitated alumina wihydate is defined as a “spent liquor”, wherein the aqueous sodie solution that is used for the predesilication originates from a mixture of an ‘aqueous sodium hydroxide soltion with « Bayer aluminate Tiquor, the aqueous sodium hydroxide solution resulting from dition of new caustic soda in water, wherein the agucots ‘odie solution is teeated in sich a manner that it has caustic concentration of between 60 g Na,Olter and 220 g Na,O/ liter and a weiaht content of carbonates, sulphates oF sulphi- tes, which, expressed as a percentage of the caustic concen- ‘ration, is less than Half @ corresponding impurities weight jeantent ofthe spent liquor, 2. The process according claim 1, whereinaqueoussodic solution has chloride weight content which, expressed as a percentage of the eavstic concentration, is less than half a chloride weight content ofthe spent liquor. 3. The process according to claim 1, wherein the prodesl cation is Cartied out using a spent liguor liguot from whic ‘most orl ofits impurities have been elimi 14. The process according to claim 1, wherein the new «aust sodas the eaustie soda thatisaddedto compensate for ‘cust soda losses in a Bayer line. '. The process according o claim 1, wherein the aquecs sodie solution contains 1 declonging liquor injected is at an injection point for supplying the aqueous sodie solution that will be used for the predesiliation