CN105073642A - Cross-linked ethylsulfonated dihydroxypropyl cellulose - Google Patents
Cross-linked ethylsulfonated dihydroxypropyl cellulose Download PDFInfo
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- 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
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/062—Digestion
- C01F7/0633—Digestion characterised by the use of additives
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/0646—Separation of the insoluble residue, e.g. of red mud
- C01F7/0653—Separation of the insoluble residue, e.g. of red mud characterised by the flocculant added to the slurry
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/144—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
- C01F7/145—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process characterised by the use of a crystal growth modifying agent other than aluminium hydroxide seed
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- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/005—Crosslinking of cellulose derivatives
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0021—Dextran, i.e. (alpha-1,4)-D-glucan; Derivatives thereof, e.g. Sephadex, i.e. crosslinked dextran
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- C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
- C08B5/14—Cellulose sulfate
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/16—Esters of inorganic acids
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/02—Dextran; Derivatives thereof
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Abstract
The invention provides methods and compositions for improving the production of alumina hydrate. The invention involves adding one or more cross-linked ethylsulfonated polysaccharides to liquor or slurry in the fluid circuit of the production process. The one or more polysaccharides include cross-linked dextran or cross-linked dihydroxypropyl cellulose. The various polysaccharides can impart a number of advantages including at least some of: greater flocculation effectiveness, increasing the maximum effective dosage, faster settling rate. The production process can be a Bayer process.
Description
Background technology
For the production of in the Bayer process of hibbsite, Bauxite Ore is pulverized typical, uses caustic solution slurrying, then boiling at high temperature and pressure.Caustic solution dissolved aluminum oxide compound, forms sodium aluminate aqueous solution.Then, the caustic alkali insoluble component of Bauxite Ore and the aqueous phase separation containing the sodium aluminate dissolved.Solid hibbsite product is precipitated out from solution and as product-collecting.
As at least in part in U.S. Patent No. 6, described in 814,873 grades, Bayer process development and the particular technology Ge Jia factory of the multiple steps for this method adopted in the industry is different, and often also hold as secret of the trade.As the more detailed of Bayer process but non-comprehensive example, the Bauxite Ore of pulverizing can be added and wherein prepare in the slurry mixer of water paste.The caustic solution that slurry composition solution is generally waste liquid (describing below) and adds.Then by this Bauxite Ore through a pulp digester or one group of pulp digester, wherein available aluminum oxide is discharged from ore as the sodium aluminate that caustic alkali is solvable.Then, use a series of flash tanks wherein reclaiming hot and cold condensate that the slurry of institute's boiling is cooled to such as about 220 °F.The aluminate feed liquid leaving flashing operation comprises insoluble solid, described solid by retain after cooking or the insoluble sludge that precipitates during boiling form.Can use " sand trap ", cyclonic separator or other devices from aluminate solution, remove thick solid particulate.If necessary, first can passing through sedimentation, then by filtering, thinner solid particulate being separated with feed liquid.
Then, the sodium aluminate solution of clarification can be cooled further and add hibbsite crystal seed wherein with induced oxidation aluminium with hibbsite form Al (OH)
3precipitation.Then hibbsite particle or crystal be classified as the fraction of multiple size and separate from liquid caustic.Liquid phase (waste liquid) will be remained turn back to initial boiling step and be used as steaming-boiling agent (digestant) after reformulating with caustic alkali.
In whole method, one of committed step is that hibbsite is from the precipitation the sodium aluminate solution of clarification.Remove insoluble solid with obtain clarify sodium aluminate feed liquid (being also called " thick liquid ") after, usually added suitable settling tank or settling tank group, and added the thin hibbsite crystal seed of recirculation wherein.In one or more settling tank, under agitation cooled and be precipitated out from feed liquid as hibbsite using induced oxidation aluminium.Fine particle hibbsite is used as crystal seed, and it is provided as the nucleation site of a part for this precipitation process and common agglomeration and growth.
Hibbsite crystal formation (nucleation of hibbsite crystal, agglomeration and growth) and precipitation thereof and to collect be the committed step of the economic recovery of the aluminum values of Bayer process.Bayer process operator makes great efforts to optimize its crystal formation and intermediate processing so that the product yield producing maximum possible from Bayer process produces the crystal of given particle size distribution simultaneously.Relatively large particle size is useful for the subsequent processing steps needed for recover aluminium metal.Undersized hibbsite crystal or particulate thing (fines) are not used in the production of aluminum metal usually, but by its recirculation to be used as fine particle hibbsite crystal seed.Therefore, the particle size of the trihydrate crystal of precipitation determines that material is finally used as product (comparatively macrocrystal) or is used as crystal seed (comparatively small-crystalline).Therefore, the trihydrate particle of different size classification and to catch be important step in Bayer process.
The separation or reclaim of the described product as Bayer process or the hibbsite crystal that is used as precipitation seed is usually realized by the combination of sedimentation, cyclonic separation, filtration and/or these technology.Thick particle is easy to sedimentation, and the slow sedimentation of thin particle.Usually, trihydrate gradation is the different size distribution corresponding to product and crystal seed by factory by two or three precipitation steps of use.Especially, in the final step of classification, usually settling vessel is used for catching the seed particles thin with sedimentation.In the precipitation step of hierarchy system, flocculation agent can be used for improve particle capture and settling velocity.
Using the overflow in last classification stage as waste back-cycling in technique.Make this waste liquid through heat exchange and evaporation, finally re-use in boiling.Therefore, any trihydrate particle being sent to overflow in this last subsidence stage can not be used as crystal seed or product in method.Such material is recirculation in process effectively, and not generation efficiency.Therefore, importantly, make the solids concn in the overflow in last classification stage minimum as much as possible thus make the maximizing efficiency of process.
As such as in U.S. Patent No. 5,041, described in 269, routine techniques utilizes the polyacrylic ester flocculation agent that adds synthesis and/or dextran flocculation agent to improve the settling character of hibbsite particle in classification process and the amount of solid reduced in waste liquid.Although be usually used in the trihydrate hierarchy system of Bayer factory by multiple flocculation agent, high expectations reduces the loss of solids that waste liquid causes as wide as possible.
Therefore, clearly ndemandseds and utilizations is existed for the classification of hibbsite precipitated in improvement Bayer process and the method for flocculation.Such improvement can improve the efficiency of producing aluminium from Bauxite Ore.
Any patent mentioned by technology described in this section is not intended to admit herein, open or other information are " prior art " relative to the present invention, unless be indicated as being clearly like that.In addition, this part should not be interpreted as meaning to make retrieval or other relevant informations not as limited in 37CFR § 1.56 (a).This document describes other feature and advantage, and it will become obvious by the following detailed description.
Invention summary
The present invention relates to the method for improvement of the Bayer process of producing aluminum oxide from Bauxite Ore.The present invention relates to use cross-linked polysaccharides, use sephadex or crosslinked dihydroxypropyl fiber usually to improve the carrying out of the unit operation in Bayer process particularly, strengthen the sedimentation of refining hibbsite crystal especially.Cross-linked cellulose comprises the mixed cellulose ethers of the covalent cross-linking mainly comprising 2,3-dihydroxypropyl ether.It also can comprise ethyl sulfonation ether.The key feature of such cross-linked cellulose ether is that the existence of 2,3-dihydroxypropyl and the covalent cross-linking that completes under homogeneous/homogeneous reaction condition cause the viscosity of the polymkeric substance dissolved in water significantly to increase.The beat all specific characteristic of the dihydroxypropyl ether of preparation like this is that it strengthens the ability of hibbsite solid flocculation from the high alkalinity Bayer process, enrichment process feed liquid (pregnantprocessliquors).
Detailed Description Of The Invention
There is provided to give a definition to determine how to explain and use in the application, the term particularly used in claim.The tissue of definition is not just to conveniently being intended to any definition to be limited to any particular category.
" substantially by ... composition " means method and composition and can comprise other step, component, composition etc., but unique condition is essential characteristic and novel feature that described other step, component and/or composition do not change in fact method and composition required for protection.
" dextran " is a kind of polysaccharide, is characterised in that it is the dextran of the α-D-1 with 1 to 3 side chain be connected with the skeleton unit of polysaccharide, 6 glucose-connections.
" dihydroxypropyl Mierocrystalline cellulose " means derivatived cellulose, is wherein added in cellulose skeleton by 1,2-dihydroxypropyl ether group.
" hydrocyclone " means to carry out classification based on the centripetal force of particle and the ratio of fluid resistance to the particle in feed liquid suspension, the device of separation or sorting, especially, this ratio is for dense and thick particle is high and for light and thin particle is low, this device has cylindrical part and the conical base at the top tangentially adding feed liquid wherein usually, and it has two outlets usually on axis: the less outlet (for underflow) in bottom and the comparatively large outlet (for overflow) at top, usually, underflow is denser or thicker fraction, and overflow is gentlier or thinner fraction.
" feed liquid " or " Bayer feed liquid " means the liquid medium through the causticity of Bayer process in industrial plants.
" polysaccharide " means to have the polymer carbohydrate of the multiple repeating units comprising monose (simplesugar), the C-O-C key formed between two monosaccharide units connected like this in polysaccharide chain is called glycosidic link, and the continuous condensating of monose (monosaccharide) unit forms polysaccharide, conventional polysaccharide is amylose starch and Mierocrystalline cellulose, both are formed by glucose monomer, polysaccharide can have the straight or branched polymer backbone comprising one or more sugar monomer, sugar monomer conventional in polysaccharide comprises glucose, semi-lactosi, pectinose, seminose, fructose, rhamnosyl (rahmnose) and wood sugar.
" slurry " means to comprise the mixture that particulate thing (it can be the solid of liquid and/or segmentation) disperses or be suspended in liquid medium wherein, when pulp jets, mine tailing (tailings) retains in the slurry and at least some concentrate (concentrate) adheres to and sprays bubble and go up and rise and leave slurry and enter foam layer on slurry, and liquid medium can be water completely, partly be water or can comprise any water not at all.
" tensio-active agent " is the term of broad sense, and it comprises anion surfactant, nonionogenic tenside, cats product and zwitterionics.May describing of tensio-active agent is shown in Kirk-Othmer, EncyclopediaofChemicalTechnology, the 3rd edition, the 8th volume, and in 900-912 page and McCutcheon ' sEmulsifiersandDetergents, both are incorporated to herein all by reference.
" thickener " or " settling vessel " means the container of the solid-liquid separation for realizing slurry, wherein usually add flocculation agent, described container is constructed and is arranged to receive slurry, retain for some time that slurry continues part (overflow) sedimentation (underflow) being downwards enough to allow the solid part of slurry away from more liquid of slurry, pour out overflow and remove underflow.Usually by thickener underflow and thickener overflow through strainer with further separating liquid and solid.
If above-mentioned definition or the implication in other descriptions mentioned Anywhere of the application and normally used implication, dictionary or to be incorporated to the implication described in the data of the application (clearly or implicitly) by reference inconsistent, so the application and term especially in claim are understood to explain according to the definition in the application or describe, instead of explain according to the definition of conventional definition, dictionary or the definition that is incorporated to by reference.In view of above, if term only can be understood according to the explanation of dictionary, if term is by Kirk-OthmerEncyclopediaofChemicalTechnology, 5th edition (2005), (by Wiley, John & Sons, Inc. publish) define, the definition in the claims of this term adopts this definition.
At least one embodiment of the present invention relates to the method for extracting hibbsite, its Bauxite Ore being included in pretreatment in alkali lye to produce the red mud solid of suspendible and the slurry of aluminate in alkali lye, then from alkali lye suspension decant red mud solid to produce decant liquid; By described decant liquid by safety filtering to remove all solids, precipitate and produce the slurry containing hibbsite solid, then by add cross-linked polysaccharides flocculate and sedimentation described in hibbsite solid.Larger trihydrate particle is made to produce the aluminum oxide of purifying, thinner particle to be again used as the crystal seed of precipitation process through calcination process.
In at least one embodiment, in the process, the preferred flocculation agent of trihydrate solid is cross-linked polysaccharides.Preferred polysaccharide comprises dextran and dihydroxypropyl Mierocrystalline cellulose.Flocculation agent adds with 0.1ppm to 100ppm.The most preferred dose scope of flocculation agent is 0.3ppm to 20ppm.Cross-linked cellulose can comprise the mixed cellulose ethers of the covalent cross-linking comprising 2,3-dihydroxypropyl ether.
In at least one embodiment, cross-linked cellulose is mainly 2,3-dihydroxypropyl ethers.In at least one embodiment, cross-linked polysaccharides/Mierocrystalline cellulose also comprises ethyl sulfonation ethers.The key feature of such cross-linked cellulose ether is existence 2,3-dihydroxypropyl.
In at least one embodiment, be Racemic glycidol for being the cellulosic reagent of dihydroxypropyl by cellulose conversion.Another suitable reagent is 3-chlorine-1,2-propylene glycol.
In at least one embodiment, further modification dihydroxypropyl Mierocrystalline cellulose is to comprise other anionic charge.This reacts by making dihydroxypropyl Mierocrystalline cellulose and sodium vinyl sulfonate and/or chloracetic acid sodium.
In at least one embodiment, crosslinked in ethyl sulfonation dihydroxypropyl Mierocrystalline cellulose is at least partly by being formed with reagent react, described reagent is Epicholorohydrin, divinylsulfone, glycerin diglycidyl ether, polyethyleneglycol diglycidylether, neopentylglycol diglycidyl ether, resorcinol diglycidyl ether, 1 such as, 2-ethylene dichloride, N, N-methylene-bisacrylamide and Isosorbide-5-Nitrae-benzoquinones and arbitrary combination thereof.Linking agent produces the key between ethyl sulfonation dihydroxypropyl each polymer chain cellulosic, and described key is stable in alkaline aqueous medium.Ehter bond as produced by Epicholorohydrin or diglycidylether belongs to the group of these keys.
In at least one embodiment, cross-linked polysaccharides is dextran.In at least one enforcement side, by dextran or dihydroxypropyl Mierocrystalline cellulose are added in the basic solution comprising sodium hydroxide, potassium hydroxide or other alkali metal or water soluble alkaline earth metal oxyhydroxide with provide pH be 11 to 14 causticization polymers soln.Then, causticization polysaccharide and suitable Bifunctionalized linking agent is made to react to produce crosslinked dihydroxypropyl Mierocrystalline cellulose.
As at least in U.S. Patent No. 6,726,845,6,740,249,3,085,853,5,008,089,5,041,269,5,091,159,5,106,599,5,346,628 and 5,716,530 and Australian Patent 5310690 and 737191 described in, use in Bayer process before dextran.
But, when compared with conventional polysaccharide or non-crosslinked analogue, observe the superior of cross-linked material activity and unexpected raising by sephadex or dihydroxypropyl cellulose chain (or thus, other suitable polysaccharide).The use of the following fact to the polysaccharide of prior art has a negative impact: the dosage increasing polysaccharide in Bayer feed liquid causes superior flocculation, but can only reach maximal dose.After reaching maximal dose, add such polysaccharide material further and usually do not produce further improved performance.When using cross-linked polysaccharides, especially, when using sephadex, superior performance (being impossible under any dose rate using conventional polysaccharide) can be reached.Unexpectedly, the maximum performance of sephadex is better than the maximum performance using conventional dextran under any dosage.In addition, for cross-linked polysaccharides, add in its lower continuation and do not cause the described dosage of further performance benefit to be increased.In addition, when glycocalix is cross-linked, observing efficiency unexpectedly increases by 50%.Such as, the composition comprising 5% sephadex can show at least equally good with the glucan composition of 10%, shows better in some cases.
U.S. Patent No. 5,049,612 and 4,339,331 instructions, in mining application examples as in sulfide ore flotation, find the performance can improving starch (traditional depressing agent) after crosslinking.Therefore, time in applying when cross-linked polysaccharides being really used for dig up mine, such as, in U.S. Patent No. 5,049,612 and 4,339, in 331, very surprisingly, in Bayer process application, the activity of dextran can be significantly improved after crosslinking.In addition, cross-linked polysaccharides have up to or at least 50% improved performance or the ability of maximum effective dose that increases polysaccharide be unexpected and novelty.In at least one embodiment, common cross-linking reagent/polysaccharide quality ratio can but be not limited to about between 0 and 0.2 change.Particularly, for Epicholorohydrin as cross-linking reagent, ratio can but be not limited between 1 and 0.1, preferably between 0.005 and 0.08 change.Measured by the soltion viscosity increase by least 10% on original solution viscosity, complete suitable being cross-linked.
In at least one embodiment, composition is added in the feed liquid in the trihydrate classification loop of described hibbsite production technique.Composition one or more position in Bayer process can be added in described feed liquid, wherein solid-liquid separation occur.
In at least one embodiment, can add in described feed liquid by composition one or more position in Bayer process, wherein it suppresses the nucleation rate of one or more hibbsite crystal in the process.
In at least one embodiment, described composition one or more position in Bayer process can be added in described feed liquid, wherein it reduces scale velocity in the process.
In at least one embodiment, can add in described feed liquid by described composition one or more position in Bayer process, wherein it promotes that red mud is clarified in the process.
In at least one embodiment, can by described composition and United States Patent (USP) 8,252, any one combination of the composition disclosed in 266 and method is added or is added according to it.
Embodiment
Can understand foregoing teachings better by reference to following examples, described embodiment presents for illustrative purposes and is not intended to limit the scope of the invention.
embodiment 1:
By 50 grams of Mierocrystalline cellulose (dissolving pulps, Bahia slurry (bahiapulp), Solucell350, cracked on the Retsch shredder using 1mm screen cloth) add in the cylindrical reaction flask of 1500ml of the overhead stirrer being equipped with duplex form.Mierocrystalline cellulose to be suspended in 800 grams of 2-methyl-2-butanols and capping flask.Suspension is kept at ambient temperature and uses bottom nitrogen purging deoxidation, simultaneously revolving stirrer under 250rpm.Bottom nitrogen purging is kept 30 minutes.Now, bottom nitrogen purging is changed into top nitrogen cover and the sodium hydroxide solution of 69.1 gram 25% is added in the cellulosic fibre slurry of suspendible.Continue stir cellulose paste and through 60 minutes, temperature be elevated to 80 DEG C gradually from envrionment temperature.69g Racemic glycidol (Aldrich) is added in the alkalinized celluloses slurry of stirring with the input speed of 1ml/ minute.The temperature of slurry to be remained at 80 DEG C and by heating or cooling to control.Mixture is kept at temperature other 20 minutes.Now, add 14 grams of sodium vinyl sulfonates (Aldrich) to intensification (80 DEG C) with the input speed of 1ml/ minute and stir mixture in.After completing interpolation, mixture is stirred other 60 minutes at 80 DEG C.The Product samples obtained at this moment is completely water miscible.With phenolphthalein (pink to clarification) for the mutatis mutandis acetic acid of indicateing arm (about 29.5g) neutralizes the slurry mixture of the ether of cellulose of alkalization.From reaction paste, rough 2,3-dihydroxypropyls-ethyl sulfonated cellulose is separated as moist press cake by filtering.Filter cake is dry in two step processes.At 60 DEG C, most of organic volatile is removed through 60 minutes in instant ventilation, drying oven.Under 0.01mmHg and temperature be no more than at 25 DEG C through the residuary water of 46 hours evaporations in raw cellulose ether.Be separated 150 grams of rough desciccates, it comprises the sodium acetate of 24% and 2, the 3-dihydroxypropyls-ethyl sulfonated cellulose of 76%.The viscosity that is rough, the plain ethereal solution of dried fibres of 2% is 36cps (30rpm, 22 DEG C, rotor LS62).
embodiment 2:
43 grams of Mierocrystalline celluloses (dissolving pulp, TobaPulpLestari, TobacellEUC94, cracked on the Retsch shredder using 1mm screen cloth) are added in the cylindrical reaction flask of 1500ml of the overhead stirrer being equipped with duplex form.Mierocrystalline cellulose to be suspended in 800 grams of 2-methyl-2-butanols and capping flask.Suspension is kept at ambient temperature and uses bottom nitrogen purging deoxidation, simultaneously revolving stirrer under 250rpm.Bottom nitrogen purging is kept 30 minutes.Now, bottom nitrogen purging is changed into top nitrogen cover and the sodium hydroxide solution of 59.5 gram 25% is added in the cellulosic fibre slurry of suspendible.Continue stir cellulose paste and through 60 minutes, temperature be elevated to 80 DEG C gradually from envrionment temperature.59g Racemic glycidol (Aldrich) is added in the alkalinized celluloses slurry of stirring with the input speed of 1ml/ minute.After completing interpolation, mixture is stirred other 60 minutes at 80 DEG C.The Product samples obtained at this moment is hardly containing the solid of suspendible.With phenolphthalein (pink to clarification) for the mutatis mutandis acetic acid of indicateing arm (about 22.6g) neutralizes the slurry mixture of the ether of cellulose of alkalization.From reaction paste, rough 2,3-dihydroxypropyl Mierocrystalline celluloses are separated as moist press cake by filtering.Filter cake is dry in two step step process.At 60 DEG C, most of organic volatile is removed through 60 minutes in instant ventilation, drying oven.Under 0.01mmHg and temperature be no more than at 25 DEG C through the residuary water of 16 hours evaporations in raw cellulose ether.Be separated 117.3 grams of rough desciccates, it comprises the sodium acetate of 26% and 2, the 3-dihydroxypropyl Mierocrystalline celluloses of 74%.The viscosity that is rough, the plain ether feed liquid of dried fibres of 2% is 36cps (30rpm, 22 DEG C, rotor LS62).
embodiment 3:
8g such as prepared in embodiment 1 and rough 2,3-dihydroxypropyls-ethyl sulfonated cellulose that viscosity is 35cps (2%, 30rpm, 23 DEG C, rotor LS62) is dissolved in 92g water.The NaOH solution of 1.02g (or as shown in the table) 50% to be added in mixture and with overhead caged impeller under 2000rpm vigorous stirring gained solution until mixture homogeneous/homogeneous phase, about 2 minutes.0.527g (or as shown in the table) Epicholorohydrin (Fluka) to be added in mixture and with overhead caged impeller under 2000rpm again vigorous stirring gained solution until mixture homogeneous, about 5 minutes.Make mixture left undisturbed overnight 16 hours to form continuous print cross linked gel.Crude reaction is diluted to 2%, with phenolphthalein be the mutatis mutandis acetic acid of indicateing arm neutralize and with Non-oxidizing biocides such as
suppress microbiological deterioration.Crosslinked 2, the 3-dihydroxypropyl-ethyl sulfonate fibers cellulose solution of preparation like this is suitable for setting accelerator as the hibbsite in Bayer process and flocculation agent.
Table 1:
EPI Epicholorohydrin
The dextrose anhydrous monomeric unit of AGU2,3-dihydroxypropyl-ethyl sulfonated cellulose
NaOH sodium hydroxide
Have studied the crosslinking reaction of ethyl sulfonation dihydroxypropyl Mierocrystalline cellulose and ethyl sulfonation dihydroxypropyl Mierocrystalline cellulose, dihydroxypropyl Mierocrystalline cellulose or Natvosol in detail.It is cellulosic crosslinked that the opinion acquired in reaction process between linking agent and dihydroxypropyl Mierocrystalline cellulose or Natvosol can be transferred directly to ethyl sulfonation dihydroxypropyl.The sheet format of correlated response is summarised in shown in following table 2 and table 3.
Table 2:
Table 2:
The result of embodiment is as follows:
1. the DS (substitution value, dihydroxypropyl number in each monomeric glucose unit in cellulose chain) of dihydroxypropyl ether of cellulose is 0.5 to 3.0.
2. the preferred DS of dihydroxypropyl ether of cellulose is 1.5 to 2.5.
3., except the DS of 1.5to2.5, dihydroxypropyl ether of cellulose also can have the MS (polysubstituted degree is attached to the average quantity of the dihydroxypropyl in each single oxyhydroxide on monomeric glucose unit in cellulose chain) being more than or equal to 1.
4. dihydroxypropyl ether of cellulose has anion substituent.
5. dihydroxypropyl ether of cellulose has anion substituent, and the DS of anionic group is greater than 0 and is less than 0.5.
6. on dihydroxypropyl ether of cellulose, preferred anion substituent is ethylsulfonic acid salt groups.
7. dihydroxypropyl ethyl sulfonated cellulose is cross-linked under homogeneous or heterogeneous condition.
8. crosslinked between each dihydroxypropyl ethyl sulfonated cellulose ether is covalency character.
9. the crosslinked of dihydroxypropyl ethyl sulfonated cellulose ether has the effect increasing its molecular weight and its soltion viscosity.
10. dihydroxypropyl ethyl sulfonated cellulose is at 30rpm before crosslinked, and the brookfield viscosity under 20 DEG C and 2% active matter content is 10cps to 100cps, and after crosslinking at 30rpm, the brookfield viscosity under 20 DEG C and 2% is 200cps to 3000cps.
11. crosslinked dihydroxypropyl ethyl sulfonated celluloses can strengthen hibbsite solid from the flocculation enrichment process feed liquid in Bayer process.
Although the present invention can be implemented in many different forms, describe in detail concrete preferred embodiment of the present invention in this article.Present disclosure is the illustrative of the principles of the inventions and is not intended to the present invention to be limited in illustrated particular.All patents herein, patent application, scientific paper and any other bibliography are incorporated to its entirety all by reference.In addition, any of some or all that multiple embodiments that are as herein described and/or that be incorporated to herein are contained in the present invention may combine.In addition, the present invention also contain get rid of clearly multiple embodiments that are as herein described and/or that be incorporated to herein any one or some outside anyly may to combine.
Above-mentioned disclosure be intended to illustrate and non exhaustive.For those of ordinary skills, this description implies many changes and substitutes.All these substitute and change is all intended to comprise within the scope of the claims, and wherein term " comprises " and meaning " including but not limited to ".Those skilled in the art will admit other equivalents of specific embodiments as herein described, these equivalents to be also intended to contain by claim.
Should be understood that all scopes disclosed herein and parameter all contain wherein comprised any and all subranges, and each numeral between endpoints.Such as, the scope " 1 to 10 " of defined should be believed to comprise any and all subranges of (with comprising 1 and 10) between minimum value 1 and maximum value 10, namely, start with minimum value 1 or larger (such as 1 to 6.1) and with maximum value 10 or less (such as, 2.3 to 9.4,3 to 8,4 to 7) terminate and be finally considered to all subranges of comprise within the scope of this each digital 1,2,3,4,5,6,7,8,9,10.Unless otherwise stated, all per-cents herein, ratio and ratio are all by weight.
So far complete of the present invention preferably and the description of alternate embodiment.Those skilled in the art should recognize, appending claims is intended to contain other equivalents being equal to specific embodiments as herein described.
Claims (12)
1. utilize Bayer process to produce a method for aluminum oxide, described method comprises the step of adding in the feed liquid or slurry of described Bayer process and comprising the composition of one or more of ethyl sulfonation cross-linked polysaccharides.
2. method according to claim 1, wherein said cross-linked polysaccharides comprises by making dextran or dihydroxypropyl Mierocrystalline cellulose or polysaccharide and linking agent carry out crosslinked to form the reaction product made by corsslinking molecular.
3. method according to claim 1, wherein said cross-linked polysaccharides is dihydroxypropyl Mierocrystalline cellulose and dihydroxypropyl number in cellulose chain in each monomeric glucose unit is 0.5 to 3.0.
4. method according to claim 1, wherein said cross-linked polysaccharides has reacted with the sodium vinyl sulfonate of q.s or chloracetic acid sodium and has replaced region to give described polysaccharide with one or more negatively charged ion.
5. method according to claim 3, wherein said dihydroxypropyl Mierocrystalline cellulose is the reaction product that Mierocrystalline cellulose and 3-chlorine-1,2-propylene glycol react.
6. method according to claim 3, wherein the brookfield viscosity of dihydroxypropyl ethyl sulfonated cellulose before crosslinked under 30rpm, 20 DEG C and 2% active matter content is 10cps to 100cps; And the brookfield viscosity after crosslinking under 30rpm, 20 DEG C and 2% active matter content is 200cps to 3000cps.
7. method according to claim 1, wherein to add to described composition in one or more position in described feed liquid thus to suppress the nucleation rate of one or more hibbsite crystal in described Bayer process.
8. method according to claim 1, wherein to add to described composition in one or more position in described feed liquid thus the scale velocity reduced in described Bayer process.
9. method according to claim 1, wherein adds to described composition in one or more position in described feed liquid to promote that the red mud in described Bayer process is clarified.
10. method according to claim 1, wherein said composition adds in the described feed liquid by described composition being added to described Bayer process and improves the productive rate being separated hibbsite from hibbsite technique.
11. methods according to claim 10, wherein said linking agent is selected from: Epicholorohydrin, dichloro glycerol, divinylsulfone, two (epoxide), phosphoryl chloride, trimetaphosphate/ester, dicarboxylic anhydride, N, N '-methylene-bisacrylamide, 2,4,6-trichloro-triazine and arbitrary combination thereof.
12. methods according to claim 1, wherein said cross-linked polysaccharides comprises by making Sclerotium gum, dextran, one of dihydroxypropyl Mierocrystalline cellulose and arbitrary combination thereof with cross-linking agents to form the reaction product made by corsslinking molecular.
Applications Claiming Priority (3)
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| US13/798,761 | 2013-03-13 | ||
| US13/798,761 US9102995B2 (en) | 2010-08-09 | 2013-03-13 | Cross-linked ethylsulfonated dihydroxypropyl cellulose |
| PCT/US2014/015538 WO2014158381A1 (en) | 2013-03-13 | 2014-02-10 | Cross-linked ethylsulfonated dihydroxypropyl cellulose |
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| CN (1) | CN105073642B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016188446A1 (en) * | 2015-05-28 | 2016-12-01 | YI, Yuan | Crosslinked polymer, hydrogel or water-based fracturing fluid comprising the same, and methods of making and using thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10427950B2 (en) | 2015-12-04 | 2019-10-01 | Ecolab Usa Inc. | Recovery of mining processing product using boronic acid-containing polymers |
| CN110678418A (en) * | 2017-02-07 | 2020-01-10 | 凯米拉公司 | Selective polysaccharide flocculant for bauxite ore dressing |
| KR20220167888A (en) * | 2021-06-15 | 2022-12-22 | 현대자동차주식회사 | A method for preparing a nanocellulose using nonionic surfactants |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88101926A (en) * | 1987-04-09 | 1988-10-26 | 诺尔科化学公司 | The application of tensio-active agent in the aluminum hydroxide precipitation process of Bayer process |
| CN1198724A (en) * | 1995-10-31 | 1998-11-11 | Cytec技术有限公司 | Removing suspended solids by addition of hydroxamated polymers in the bayer process |
| CN1324328A (en) * | 1998-08-17 | 2001-11-28 | 科马尔柯铝制品有限公司 | Feed processing for improved alumina process performance |
| CN1594094A (en) * | 2004-06-25 | 2005-03-16 | 中国铝业股份有限公司 | Process for producing sand alumina by Bayer precipitation process |
| CN1772620A (en) * | 2004-11-10 | 2006-05-17 | 赵中伟 | Symmetrical Bayer process of decomposing bauxite |
| CN1911805A (en) * | 2006-09-05 | 2007-02-14 | 中国铝业股份有限公司 | Production of aluminium oxide using Bayer method |
| CN101264906A (en) * | 2008-04-25 | 2008-09-17 | 河南未来铝业（集团）有限公司 | Method for producing aluminum hydroxide or aluminum oxide by Bayer process |
| WO2012021375A2 (en) * | 2010-08-09 | 2012-02-16 | Nalco Company | The recovery of alumina trihydrate during the bayer process using cross-linked polysaccharides |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3742104A1 (en) * | 1987-12-11 | 1989-06-22 | Wolff Walsrode Ag | SULFOETHYL CELLULOSE WITH EXCELLENT SOLUTION QUALITY AND METHOD FOR THE PRODUCTION THEREOF |
| DE4113892A1 (en) * | 1991-04-27 | 1992-10-29 | Wolff Walsrode Ag | WATER-SOLUBLE SULFOETHYLCELLULOSE ETHER WITH A VERY GOOD SOLUTION QUALITY AND METHOD FOR THE PRODUCTION THEREOF |
| US5254403A (en) * | 1992-04-23 | 1993-10-19 | Xerox Corporation | Coated recording sheets |
| US5478477A (en) * | 1994-11-04 | 1995-12-26 | Nalco Chemical Company | Use of alginates to treat bauxite red mud |
| US7138472B2 (en) * | 2001-01-29 | 2006-11-21 | Nalco Company | High molecular weight polymers containing pendant salicylic acid groups for clarifying bayer process liquors |
| US8252266B2 (en) * | 2010-08-09 | 2012-08-28 | Nalco Company | Recovery of alumina trihydrate during the bayer process using scleroglucan |
-
2014
- 2014-02-10 JP JP2016500226A patent/JP2016517385A/en active Pending
- 2014-02-10 WO PCT/US2014/015538 patent/WO2014158381A1/en active Application Filing
- 2014-02-10 AU AU2014242325A patent/AU2014242325B2/en active Active
- 2014-02-10 CN CN201480013653.1A patent/CN105073642B/en active Active
- 2014-02-10 BR BR112015022243-9A patent/BR112015022243B1/en active IP Right Grant
- 2014-02-10 CA CA2904522A patent/CA2904522C/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88101926A (en) * | 1987-04-09 | 1988-10-26 | 诺尔科化学公司 | The application of tensio-active agent in the aluminum hydroxide precipitation process of Bayer process |
| CN1198724A (en) * | 1995-10-31 | 1998-11-11 | Cytec技术有限公司 | Removing suspended solids by addition of hydroxamated polymers in the bayer process |
| CN1324328A (en) * | 1998-08-17 | 2001-11-28 | 科马尔柯铝制品有限公司 | Feed processing for improved alumina process performance |
| CN1594094A (en) * | 2004-06-25 | 2005-03-16 | 中国铝业股份有限公司 | Process for producing sand alumina by Bayer precipitation process |
| CN1772620A (en) * | 2004-11-10 | 2006-05-17 | 赵中伟 | Symmetrical Bayer process of decomposing bauxite |
| CN1911805A (en) * | 2006-09-05 | 2007-02-14 | 中国铝业股份有限公司 | Production of aluminium oxide using Bayer method |
| CN101264906A (en) * | 2008-04-25 | 2008-09-17 | 河南未来铝业（集团）有限公司 | Method for producing aluminum hydroxide or aluminum oxide by Bayer process |
| WO2012021375A2 (en) * | 2010-08-09 | 2012-02-16 | Nalco Company | The recovery of alumina trihydrate during the bayer process using cross-linked polysaccharides |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016188446A1 (en) * | 2015-05-28 | 2016-12-01 | YI, Yuan | Crosslinked polymer, hydrogel or water-based fracturing fluid comprising the same, and methods of making and using thereof |
| US20180273649A1 (en) | 2015-05-28 | 2018-09-27 | Yuan Yi | Crosslinked polymer, hydrogel or water-based fracturing fluid comprising the same, and methods of making and using thereof |
| US10308726B2 (en) | 2015-05-28 | 2019-06-04 | Yuan Yi | Crosslinked polymer, hydrogel or water-based fracturing fluid comprising the same, and methods of making and using thereof |
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| BR112015022243A2 (en) | 2017-07-18 |
| CA2904522C (en) | 2020-06-30 |
| AU2014242325A1 (en) | 2015-11-05 |
| AU2014242325B2 (en) | 2016-12-15 |
| JP2016517385A (en) | 2016-06-16 |
| BR112015022243B1 (en) | 2022-02-15 |
| CN105073642B (en) | 2017-06-20 |
| CA2904522A1 (en) | 2014-10-02 |
| WO2014158381A1 (en) | 2014-10-02 |
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