CN105073642B - Ethyl dihydroxypropyl sulfonated crosslinked cellulose - Google Patents

Ethyl dihydroxypropyl sulfonated crosslinked cellulose Download PDF

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CN105073642B
CN105073642B CN 201480013653 CN201480013653A CN105073642B CN 105073642 B CN105073642 B CN 105073642B CN 201480013653 CN201480013653 CN 201480013653 CN 201480013653 A CN201480013653 A CN 201480013653A CN 105073642 B CN105073642 B CN 105073642B
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CN105073642A (en )
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海因里希·E·博德
约翰·D·基尔德
王菁
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纳尔科公司
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/02Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06Preparation 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
    • C01F7/062Digestion
    • C01F7/0633Digestion characterised by the use of additives
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/02Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06Preparation 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
    • C01F7/0646Separation of the insoluble residue, e.g. red mud
    • C01F7/0653Separation of the insoluble residue, e.g. red mud characterised by the flocculant added to the slurry
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/02Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/144Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
    • C01F7/145Aluminium 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 a crystal growth modifying agent other than aluminium hydroxide seed
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/005Crosslinking of cellulose derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009Homoglycans, 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
    • C08B37/0021Dextran, i.e. (alpha-1,4)-D-glucan; Derivatives thereof, e.g. Sephadex, i.e. crosslinked dextran
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C08B5/14Cellulose sulfate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • C08L1/16Esters of inorganic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/02Dextran; Derivatives thereof

Abstract

本发明提供了用于改进水合氧化铝生产的方法和组合物。 The present invention provides an improved method of producing alumina hydrate and compositions. 本发明包括将一种或更多种交联乙基磺化多糖添加到生产方法的流体回路中的料液或浆料中。 The present invention comprises the addition of one or more of ethyl sulfonated crosslinked polysaccharide production process fluid circuit to the feed liquid or slurry. 所述一种或更多种多糖包括交联葡聚糖或交联二羟丙基纤维素。 The polysaccharide comprises one or more cross-linked dextran or cross-linked hydroxypropylcellulose two. 多种多糖可赋予许多优点,包括以下的至少一些:絮凝效率更高、最大有效剂量增加、沉降速度更快。 More polysaccharides can be given a number of advantages, including at least some of the following: higher flocculation efficiency, increase the maximum effective dose, settling velocity faster. 所述生产方法可以是拜耳法。 The production process may be a Bayer process.

Description

交联的乙基磺化二羟丙基纤维素 Ethyl dihydroxypropyl sulfonated crosslinked cellulose

背景技术 Background technique

[0001] 在典型的用于生产三水合氧化铝的拜耳法中,铝土矿矿石被粉碎,用苛性碱溶液制浆,然后在高温和高压下蒸煮。 [0001] In a typical for the production of alumina trihydrate Bayer process, bauxite ore is pulverized, slurried with a caustic alkali solution, and then cooked at elevated temperature and pressure. 苛性碱溶液溶解铝氧化物,形成铝酸钠水溶液。 Caustic solution dissolves oxides of aluminum, forming an aqueous solution of sodium aluminate. 然后,铝土矿矿石的苛性碱不溶性组分与含有溶解的铝酸钠的水相分离。 Then, caustic bauxite ore with a water insoluble component containing the dissolved sodium aluminate phase separation. 使固体三水合氧化铝产物从溶液中沉淀出来并作为产品收集。 The solid alumina trihydrate product is precipitated out of solution and collected as product.

[0002] 如至少部分地在美国专利No.6,814,873等中所描述的,拜耳法不断发展并且业内采用的针对该法的多个步骤的特定技术各家工厂不同,而且经常还作为商业秘密持有。 [0002] The at least partially in U.S. Patent No.6,814,873 and the like as described, different Bayer process industry and the development of specific techniques employed for various plant plurality of steps of the process, but also often held as trade secrets . 作为拜耳法的更详细但非全面的实例,可将粉碎的铝土矿矿石加入其中制备水性浆料的浆料混合器中。 As the Bayer process in more detail, but not a comprehensive example, pulverized bauxite ore may be added to the slurry mixer where an aqueous slurry is prepared in. 浆料组成溶液通常为废液(以下描述)和添加的苛性碱溶液。 Composition of the waste solution is generally a slurry (described below) and added caustic solution. 然后将该铝土矿矿石经过一个蒸煮器或一组蒸煮器,其中将可用的氧化铝作为苛性碱可溶的铝酸钠从矿石中释放出来。 The bauxite ore is then passed through a digester or a group of the digester, wherein the available alumina as caustic-soluble sodium aluminate and released from the ore. 然后,使用其中回收热和冷凝物的一系列闪蒸罐将所蒸煮的浆料冷却至例如约220°F。 Then, using the recovered heat and wherein a series of flash condensate tank The cooked slurry was cooled to e.g. about 220 ° F. 离开闪蒸操作的铝酸盐料液包含不溶性固体,所述固体由在蒸煮之后保留的或在蒸煮期间沉淀的不溶性残渣组成。 Leaving the flashing operation of the aluminate liquor comprising insoluble solids, the solids retained by the cooking or after cooking during the insoluble residue precipitated composition. 可使用“集砂器”、旋风分离器或其他装置从铝酸盐溶液中移除粗的固体颗粒。 Using "sand collecting device" cyclone or other means for removing solid particles from a crude aluminate solution. 如有必要,可首先通过沉降,然后通过过滤将较细的固体颗粒与料液分离。 If necessary, first by settling and then the finer solid particles feed liquid separation by filtration.

[0003] 然后,可将澄清的铝酸钠溶液进一步冷却并向其中加入三水合氧化铝晶种以诱导氧化铝以三水合氧化铝形式Al (OH) 3沉淀。 [0003] may then be clarified sodium aluminate solution is further cooled and wherein the alumina trihydrate seed crystals were added to induce a form of alumina trihydrate Al (OH) 3 precipitate. 然后将三水合氧化铝颗粒或晶体分级为多个尺寸的级分并从苛性碱液中分离出来。 Then alumina trihydrate particles or crystals of a plurality of size graded and separated fractions from the caustic lye. 将残留液相(废液)返回到初始的蒸煮步骤并在用苛性碱重新组成之后用作蒸煮剂(digestant)。 The residual liquid (waste liquid) is returned to the initial digestion step and used as a cooking agent (digestant) after reconstitution with caustic.

[0004] 在整个方法中,关键步骤之一是三水合氧化铝从澄清的铝酸钠溶液中的沉淀。 [0004] Throughout the process, a key step is the precipitation of alumina trihydrate from the clarified sodium aluminate solution. 在移除不溶性固体以得到澄清的铝酸钠料液(还称为“粗液”)之后,通常将其加入合适的沉淀池或沉淀池组,并向其中加入再循环的细的三水合氧化铝晶种。 After the sodium aluminate solution to remove the insoluble solid material to yield a clear (also referred to as "thick liquid"), which is generally added suitable precipitating or settling group added thereto recycled fine oxide trihydrate aluminum seed. 在一个或多个沉淀池中,在搅拌下将其冷却以诱导氧化铝作为三水合氧化铝从料液中沉淀出来。 In one or more sedimentation tank, cooled with stirring to induce the alumina as alumina trihydrate is precipitated from the feed solution. 细颗粒三水合氧化铝用作晶种,其提供作为该沉淀过程的一部分之成核位点和共同附聚以及生长。 Fine particles of alumina trihydrate is used as a seed crystal, which is provided as part of nucleation sites for the precipitation process and co-agglomeration and growth.

[0005] 三水合氧化铝晶体形成(三水合氧化铝晶体的成核、附聚和生长)及其沉淀和收集是拜耳法的铝值之经济回收的关键步骤。 [0005] Alumina trihydrate crystal formation (the nucleation of alumina trihydrate crystals, agglomeration and growth) and the precipitate was collected and is a key step in the economic recovery of aluminum values ​​of the Bayer process. 拜耳法操作者努力优化其晶体形成和沉淀方法以便从拜耳法中产生最大可能的产品收率同时产生给定颗粒尺寸分布的晶体。 Bayer process operators strive to optimize their crystal formation and precipitation methods so as to produce the greatest possible product yield from the Bayer process while producing crystals of a given particle size distribution. 相对大的颗粒尺寸对于回收铝金属所需的后续处理步骤是有益的。 A relatively large particle size is beneficial to subsequent processing steps required to recover aluminum metal. 小尺寸的三水合氧化铝晶体或细粒物(fines)通常不用于铝金属的生产,而是将其再循环以用作细颗粒三水合氧化铝晶种。 Small size alumina trihydrate crystals or fine particles thereof (fines) typically is not used for the production of aluminum metal, but it is recycled as fine particles of alumina trihydrate seed. 因此,沉淀的三水合物晶体的颗粒尺寸决定材料最终被用作产品(较大晶体)还是用作晶种(较小晶体)。 Thus, the particle size of the precipitated trihydrate crystals are used as a product material is finally determined (large crystals) or as a seed (a small crystal). 因此,不同尺寸的三水合物颗粒的分级和捕获是拜耳法中的重要步骤。 Thus, classification and capture trihydrate particles of different sizes is an important step in the Bayer process.

[0006] 所述作为拜耳法的产品或用作沉淀晶种的三水合氧化铝晶体的分离或回收通常通过沉降、旋风分离、过滤和/或这些技术的组合来实现。 [0006] The Bayer process as a product or as a precipitated alumina trihydrate seed crystals are usually recovered by sedimentation or separation, cyclone separation, and / or a combination of these techniques to achieve filtering. 粗的颗粒易于沉降,而细的颗粒缓慢沉降。 Coarse particles tend to settle, the fine particles settle slowly. 通常,工厂将使用两个或三个沉降步骤来将三水合物颗粒分级为对应于产品和晶种的不同尺寸分布。 Typically, two or three plants will be used for the settling step trihydrate particles are classified to correspond to different products and seed size distribution. 特别地,在分级的最后步骤中,通常将沉降器用于捕获和沉降细的晶种颗粒。 In particular, the final step in the hierarchy, it is generally used to capture the settling and settling fine seed particles. 在分级系统的沉降步骤中,可将絮凝剂用于提高颗粒捕获和沉降速度。 In the settling step grading system, the flocculant may be used to capture and enhance the particle settling velocity.

[0007] 将最后分级阶段的溢流作为废液返回到工艺中。 [0007] The final ranking stage overflow is returned to the process as a waste. 使该废液经过热交换和蒸发,最后在蒸煮中再使用。 The waste passes through the heat exchanger and the evaporator, and finally in the cook. 因此,在该最后沉降阶段中传送到溢流的任何三水合物颗粒在方法中将不会用作晶种或产品。 Thus, the final transfer stage to settle any overflow trihydrate particles as in the method does not seed or product. 这样的材料有效地在工艺中再循环,而不产生效率。 Such materials are efficiently recycled in the process, without generation efficiency. 因此,重要的是,使最后分级阶段的溢流中的固体浓度尽可能地最低从而使过程的效率最大化。 Therefore, it is important that the overflow solids concentration in the final ranking stage as much as possible so that a minimum to maximize the efficiency of the process.

[0008] 如例如在美国专利No. 5,041,269中所述的,常规技术利用添加合成的聚丙烯酸酯絮凝剂和/或葡聚糖絮凝剂来改善在分级过程中三水合氧化铝颗粒的沉降特性并降低废液中的固体量。 [0008] As described in U.S. Patent No. 5,041,269, the use of conventional techniques, for example, adding a synthetic polyacrylate flocculant and / or flocculating agent to improve the dextran during the classification of alumina trihydrate particles settling properties and reduce the amount of solids in the waste. 虽然通常将多种絮凝剂用于拜耳工厂的三水合物分级系统中,但是高度期望尽可能大地降低废液造成的固体损失。 Although typically more plant flocculant for Bayer trihydrate classification system, but is highly desirable to reduce as much as possible due to loss of solids waste.

[0009] 因此,对于改进拜耳法中所沉淀的三水合氧化铝的分级和絮凝的方法存在清楚的需求和利用。 [0009] Accordingly, there is a clear need for an improved and using the Bayer process alumina trihydrate precipitated and flocculated classification methods. 这样的改进可提高从铝土矿矿石中生产铝的效率。 Such improvements can improve the efficiency of the production of aluminum from bauxite ore.

[0010] 在这部分所述的技术不旨在承认本文所提及的任何专利、公开或其他信息相对于本发明为“现有技术”,除非明确地指明为那样。 Any Patent [0010] The techniques described in this section is not intended to recognize mentioned herein, or other information disclosed in the present invention is "prior art", unless expressly stated with respect to that. 此外,这部分不应被解释为意指已经做出检索或者没有如37CFR§1.56 (a)中限定的其他相关信息存在。 In addition, this section should not be construed to mean that has been made or no other relevant information retrieval as defined in (a) in the presence of 37CFR§1.56. 本文描述了另外的特征和优点, 并且其通过以下的详细描述将变得明显。 Additional features described herein and advantages, and it will become apparent from the following detailed description.

[0011] 发明简述 [0011] SUMMARY OF THE INVENTION

[0012] 本发明涉及用于改进从铝土矿矿石生产氧化铝的拜耳法的方法。 [0012] The present invention relates to an improved process for producing alumina from bauxite ore used in the Bayer process. 本发明涉及使用交联多糖,具体地使用交联葡聚糖或交联二羟丙基纤维素来改善拜耳法中的单元操作的进行,特别地来增强精制三水合氧化铝晶体的沉降。 The present invention relates to crosslinked polysaccharides, particularly crosslinked or crosslinked dextran dihydroxypropyl cellulose to improve the operation of the Bayer process unit, in particular to enhance the settling purified by alumina trihydrate crystals. 交联纤维素包括主要包含2,3_二羟丙基醚的共价交联的混合纤维素醚。 It comprises mainly cross-linked cellulose ether comprising mixing cellulose ether 2,3_-dihydroxypropyl covalently crosslinked. 其还可包括乙基磺化醚。 It may also include sulfonated ethyl ether. 这样的交联纤维素醚的关键特征为2,3_二羟丙基的存在以及在均质/均相反应条件下完成的共价交联导致在水中溶解的聚合物的粘度显著增加。 Such a key feature of cross-linked cellulose ether is present in 2,3_ dihydroxypropyl covalently performed under homogeneous / heterogeneous reaction conditions, the viscosity of the crosslinked polymer dissolved in water is significantly increased. 如此制备的二羟丙基醚的出人意料的独特特征为其增强三水合氧化错固体从拜耳法中的高碱性、富集过程料液(pregnant process liquors)中絮凝的能力。 Surprisingly unique characteristics dihydroxypropyl ether thus prepared for its ability to enhance the error trihydrate from Bayer process solids overbased, enrichment process feed solution (pregnant process liquors) in flocculation.

[0013] 发明详述 [0013] DETAILED DESCRIPTION

[0014] 提供以下定义来确定如何解释本申请中所使用的,特别是权利要求中所使用的术语。 [0014] The following definitions are provided to determine how to interpret the term as used in this application, especially as used in the claims. 定义的组织仅仅为了方便而并不旨在将任何定义限制于任何特定类别。 Defined organization for convenience only and are not intended to define any restrictions on any particular category.

[0015] “基本上由......组成”意指方法和组合物可包括另外的步骤、组分、成分等,但是唯一的条件是所述另外的步骤、组分和/或成分并不实质上改变所要求保护的方法和组合物的基本特征和新颖特征。 [0015] "...... consisting essentially consisting of" means that the methods and compositions may include additional steps, components, ingredients, etc., but the only requirement is that the additional steps, components and / or ingredients It does not materially alter the basic characteristics of the claimed features and novel methods and compositions.

[0016] “葡聚糖”是一种多糖,特征在于其是具有与多糖的骨架单元连接的1至3个侧链的a-D_l,6葡萄糖-连接的葡聚糖。 [0016] "glucan" is a polysaccharide, characterized in that it is a-D_l side chain having from 1 to 3 connected to the backbone units of the polysaccharide, glucose 6 - linked dextran.

[0017] “二羟丙基纤维素”意指纤维素衍生物,其中将1,2_二羟丙基醚基团添加到纤维素骨架上。 [0017] "two hydroxypropyl cellulose" means a cellulose derivative, wherein the added 1,2_-dihydroxypropyl ether groups onto the cellulose backbone.

[0018] “水力旋流器”意指基于颗粒的向心力与流体阻力的比率对料液混悬液中的颗粒进行分级、分离或分选的装置,特别地,该比率对于稠密的且粗的颗粒高而对于轻的且细的颗粒低,该装置通常具有在其中切向地加入料液的顶部的圆柱形部分和圆锥底部,并且其通常在轴线上具有两个出口:在底部的较小出口(用于底流)和在顶部的较大出口(用于溢流),通常,底流是较稠密或较粗的级分,而溢流是较轻或较细的级分。 [0018] "Hydrocyclones" means a centripetal force based on the particles and fluid resistance ratio of the feed solution classifying particles in suspension, separating or sorting apparatus, in particular, the ratio of the coarse and dense high for low light particles and fine particles, the device having a generally cylindrical portion and a bottom wherein the cone tangentially at the top of the feed solution is added, and it typically has two outlets on an axis: smaller at the bottom an outlet (for underflow) and a larger outlet (for overflow) at the top, usually, a denser or underflow coarser fraction and a lighter or overflow is the finer fractions.

[0019] “料液”或“拜耳料液”意指在工业设施中经过拜耳法的苛性的液体介质。 [0019] "feed solution" or "Bayer feed liquid" means a liquid medium through caustic Bayer process in an industrial facility.

[0020] “多糖”意指具有包含单糖(simple sugar)的多个重复单元的聚合碳水化合物,在多糖链中在两个这样连接的单糖单元之间形成的COC键称为糖苷键,并且单糖(monosaccharide)单元的连续缩合形成多糖,常用的多糖是直链淀粉和纤维素,两者均由葡萄糖单体构成,多糖可具有包含一个或更多个糖单体的直链或支链聚合物骨架,在多糖中常用的糖单体包括葡萄糖、半乳糖、阿拉伯糖、甘露糖、果糖、鼠李糖(rahmnose)和木糖。 [0020] "polysaccharide" means a polymeric carbohydrate having a plurality of repeating units comprises a monosaccharide (simple sugar) is, COC bonds in the polysaccharide chain is formed between two such linked monosaccharide units called glycosidic bond, and continuously condensed monosaccharide (monosaccharide) means forming a polysaccharide, the polysaccharide is a common amylose and cellulose, both composed of glucose monomers, polysaccharides may have contain one or more sugar monomers linear or branched polymer backbone chains, commonly used in the sugar monomers polysaccharides include glucose, galactose, arabinose, mannose, fructose, rhamnose (rahmnose) and xylose.

[0021] “浆料”意指包含细粒物(其可以是液体和/或细分的固体)分散或混悬于其中的液体介质之混合物,当衆料喷射时,尾矿(tailings)保留在楽;料中而至少一些精矿(concentrate)粘附于喷射泡上并上升离开楽;料进入楽:料之上的泡沫层,液体介质可以完全是水、部分是水或可一点也不包含任何水。 [0021] "slurry" means a composition comprising fine particles (which may be liquid and / or finely divided solid) is dispersed or suspended in a mixture of the liquid medium in which, when the public injection material, tailings (Tailings) Reserved in yue; at least some of the feed concentrate (concentrate) is adhered to and lifted off the injection Paoshang yue; material enters yue: a foam layer, the liquid above the dielectric material may be entirely water, or may be part of the water is not at contain any water.

[0022] “表面活性剂”是广义的术语,其包括阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂和两性离子表面活性剂。 [0022] "Surfactant" is a broad term that includes anionic surfactants, nonionic surfactants, cationic surfactants and zwitterionic surfactants. 表面活性剂的可能描述示于Kirk-Othmer, Encyclopedia of Chemical Technology,第3版,第8卷,第900-912页和McCutcheon's Emulsifiers and Detergents中,两者均通过引用并入本文。 Surfactants may be described is shown in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 8, pp. 900-912, and in McCutcheon's Emulsifiers and Detergents, both incorporated herein by reference.

[0023] “增稠器”或“沉降器”意指用于实现浆料的固-液分离的容器,其中通常添加絮凝剂,所述容器被构造并布置成接收浆料,保留浆料持续足以允许浆料的固体部分远离浆料的更多液体的部分(溢流)向下沉降(底流)的一段时间,倒出溢流并移除底流。 [0023] "thickener" or "settling" means a solid to the slurry to achieve - liquid separation vessel, wherein the flocculant is typically added, the container is constructed and arranged to receive the slurry, retaining the slurry continuously part of a period of time sufficient to allow more liquid away from the solid portion of the slurry slurry (overflow) settle down (underflow) is decanted and removed underflow overflow. 通常将增稠器底流和增稠器溢流经过过滤器以进一步分离液体与固体。 Typically the thickener and thickener underflow overflow through a filter to further separate liquids from solids.

[0024] 如果上述定义或在本申请其他任何地方所提及的描述与通常使用的含义、词典中的含义或者在通过引用并入本申请的资料中所述的含义(明确地或暗含地)不一致,那么本申请且尤其是权利要求中的术语被理解为根据本申请中的定义或描述来解释,而不是根据常用的定义、词典的定义或通过引用并入的定义来解释。 [0024] If in the present application as defined above or elsewhere mentioned meanings commonly used and description of the meaning or dictionary (explicitly or implicitly) by data incorporated herein by reference in the meaning of inconsistent, then the present application and especially in the claims the term is understood to be interpreted according to the definition or description of the present application, rather than according to a common definition, dictionary definition or definitions explained by reference incorporated. 鉴于上文,如果术语仅可以按照字典的解释被理解,如果术语由Kirk-Othmer Encyclopedia of Chemical Technology,第5 版(2005),(由Wiley,John&Sons,Inc.出版)来定义,该术语在权利要求中的定义采用该定义。 In view of the above, if the term can only be understood in accordance with the interpretation dictionary, if a term in the Kirk-Othmer Encyclopedia of Chemical Technology, 5th Edition (2005), (manufactured by Wiley, John & amp; Sons, Inc published) is defined, the term It is defined in the claims use of this definition.

[0025] 本发明的至少一个实施方案涉及用于提取三水合氧化铝的方法,其包括在碱液中蒸煮预处理的铝土矿矿石以产生在碱液中混悬的赤泥固体与铝酸盐的浆料,然后从碱液混悬液中倾析赤泥固体以产生倾析液;将所述倾析液通过安全过滤以移除所有固体,沉淀并产生含有三水合氧化铝固体的浆料,然后通过添加交联多糖来絮凝和沉降所述三水合氧化铝固体。 [0025] at least one embodiment of the present invention relates to a method for extracting alumina trihydrate, which comprises bauxite ore in the alkali solution to produce a pre-cooked in the suspended red mud solids and alkali aluminate the salt slurry was then poured from the alkaline suspension to produce an analysis of red mud solids was decanted; the decanted solution by filtration to remove any solids safe, and produce slurry containing precipitated alumina trihydrate solids material, then the crosslinked polysaccharide by the addition to flocculation and sedimentation, the solid alumina trihydrate. 使较大的三水合物颗粒经过煅烧过程以产生纯化的氧化铝而将较细的颗粒重新用作沉淀过程的晶种。 So that particles larger trihydrate calcination process to produce a purified alumina and the finer particles are used as seeds to re-precipitation process.

[0026] 在至少一个实施方案中,在所述方法中,三水合物固体的优选絮凝剂为交联多糖。 [0026] In at least one embodiment, in the method, preferably the flocculant is a trihydrate solid crosslinked polysaccharide. 优选的多糖包括葡聚糖和二羟丙基纤维素。 Preferred polysaccharides include dextran and dihydroxypropyl cellulose. 絮凝剂以〇. Ippm至IOOppm添加。 Flocculant billion. Ippm to IOOppm added. 絮凝剂的最优选剂量范围为〇.3ppm至20ppm。 The most preferred dosage range is 〇.3ppm flocculant to 20ppm. 交联纤维素可包括包含2,3_二羟丙基醚的共价交联的混合纤维素醚。 It may comprise cross-linked cellulose ether comprising mixing cellulose ether 2,3_-dihydroxypropyl covalently crosslinked.

[0027] 在至少一个实施方案中,交联纤维素主要为2,3_二羟丙基醚类。 [0027] In at least one embodiment, the crosslinked cellulose ethers predominantly 2,3_-dihydroxypropyl. 在至少一个实施方案中,交联多糖/纤维素还包括乙基磺化醚类。 In at least one embodiment, the crosslinked polysaccharide / ethyl further comprising a sulfonated cellulose ethers. 这样的交联纤维素醚的关键特征是存在2, 3-二羟丙基。 Such crosslinked cellulose ethers key feature is the presence of 2, 3-dihydroxypropyl.

[0028] 在至少一个实施方案中,用于将纤维素转化为二羟丙基纤维素的试剂是缩水甘油。 [0028] In at least one embodiment, reagents for converting the cellulose is hydroxypropylcellulose two glycidol. 另一个合适的试剂是氯,2-丙二醇。 Another suitable agent is chlorine, propanediol.

[0029] 在至少一个实施方案中,进一步改性二羟丙基纤维素以包含另外的阴离子电荷。 [0029] In at least one embodiment, is further modified to comprise two hydroxypropylcellulose additional anionic charge. 这可通过使二羟丙基纤维素与乙烯基磺酸钠和/或氯代乙酸钠反应来完成。 This may be accomplished by two hydroxypropyl cellulose and sodium vinyl sulfonate and / or sodium chloroacetate reaction.

[0030] 在至少一个实施方案中,在乙基磺化二羟丙基纤维素中的交联是至少部分通过与试剂反应形成的,所述试剂例如表氯醇、二乙烯基砜、甘油二缩水甘油醚、聚乙二醇二缩水甘油醚、新戊二醇二缩水甘油醚、间苯二酚二缩水甘油醚、1,2_二氯乙烷、N,N-亚甲基双丙烯酰胺和1,4_苯醌及其任意组合。 [0030] In at least one embodiment, two crosslinking sulfonated ethyl hydroxypropyl cellulose is at least partially formed by reaction with a reagent, the reagent such as epichlorohydrin, divinyl sulfone, diglycerides ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, 1,2_-dichloroethane, N, N- methylene-bis-acrylamide 1,4_ benzoquinone and any combination thereof. 交联剂产生乙基磺化二羟丙基纤维素的各个聚合物链之间的键,所述键在碱性水介质中是稳定的。 Bonds between a crosslinking agent to produce individual polymer chains sulfonated ethyl dihydroxypropyl cellulose, the alkaline aqueous medium bond is stable. 如由表氯醇或二缩水甘油醚产生的醚键属于这些键的组。 The ether linkages resulting from epichlorohydrin or diglycidyl ethers of these bonds belonging to the group.

[0031] 在至少一个实施方案中,交联多糖是葡聚糖。 [0031] In at least one embodiment, the crosslinked polysaccharide is dextran. 在至少一个实施方中,通过将葡聚糖或二羟丙基纤维素添加到包含氢氧化钠、氢氧化钾或其他碱金属或水溶性碱土金属氢氧化物的碱性溶液中以提供pH为11至14的苛化聚合物溶液。 In at least one embodiment Fang, by adding dextran or hydroxypropylcellulose into two basic solution containing sodium hydroxide, potassium hydroxide or other soluble alkali metal or alkaline earth metal hydroxide to provide a pH causticizing polymer solution was 11 to 14. 然后,使苛化多糖与适当的双官能化交联剂反应来产生交联二羟丙基纤维素。 Then, the causticization reaction of difunctional crosslinking agent to produce a polysaccharide with a suitable crosslinking dihydroxypropyl cellulose.

[0032] 如至少在美国专利No ·6,726,別5、6,740,、3,〇85,853、5,0〇8,〇89、5,041,269、 5,091,159、5,106,599、5,346,628和5,716,530 以及澳大利亚专利5310690和737191 中所述,葡聚糖之前已在拜耳法中使用。 [0032] The at least in U.S. Patent No · 6,726, do not 5,6,740,, 3, 〇85,853,5,0〇8, 〇89,5,041,269, 5,091,159,5,106,599, 5,346,628 and 5,716,530 and 5,310,690 and Australian Patent No. 737,191 in the, has been used in the Bayer process prior to dextran.

[0033] 然而,当与常规多糖或非交联类似物相比时,通过交联葡聚糖或二羟丙基纤维素链(或者就此而言,其他合适的多糖)观察到交联材料活性的优越和意外提高。 [0033] However, when compared to conventional crosslinked polysaccharide or the like, or by cross-linked dextran chains dihydroxypropyl cellulose (or for that matter, other suitable polysaccharide) active crosslinking material was observed superior and unexpected increase. 以下事实对现有技术的多糖的使用产生不利影响:在拜耳料液中增加多糖的剂量导致优越的絮凝,不过只能达到最大剂量。 The fact that the use of polysaccharides to produce the prior art adverse effects: increasing doses of polysaccharide in Bayer feed solution results in superior flocculation, but can only reach a maximum dose. 在达到最大剂量之后,进一步添加这样的多糖材料通常不产生进一步的性能改善。 After the maximum dose, the addition of such further polysaccharide materials do not typically produce additional performance improvements. 当使用交联多糖时,特别地,当使用交联葡聚糖时,可达到优越的性能(在使用常规多糖的任意剂量率下是不可能的)。 When a crosslinked polysaccharide, in particular, when a cross-linked dextran, can achieve superior performance (it is impossible to use in any conventional dosage rate polysaccharides). 出乎意料地,交联葡聚糖的最大性能优于在任意剂量下使用常规葡聚糖的最大性能。 Surprisingly, cross-linked dextran maximum performance superior to the maximum performance in any conventional dosage dextran. 此外,对于交联多糖,在其下继续添加并不导致进一步的性能益处的所述剂量被增加。 In addition, crosslinked polysaccharide, in which case the dosage does not lead to continue to add a further benefit is increased performance. 此外,当多糖被交联时,观察到效率意外地增加50%。 Further, when the polysaccharide is crosslinked, unexpectedly observed to increase by 50% efficiency. 例如, 包含5%交联葡聚糖的组合物可表现得至少与10%的葡聚糖组合物一样好,在一些情况下表现得更好。 For example, containing 5% dextran crosslinked composition may behave at least as good as 10% dextran composition, better performance in some cases.

[0034] 美国专利No. 5,049,612和4,339,331教导,在采矿应用例如硫化物矿石浮选中,发现在交联之后可改善淀粉(传统的浮选抑制剂)的性能。 [0034] U.S. Pat. No. 5,049,612 and 4,339,331 teach, for example in mining applications sulfide ore flotation found after crosslinking may improve the performance of the starch (conventional flotation inhibitor). 因此,当将交联多糖真的用于采矿应用中时,例如在美国专利如.5,049,612和4,339,331中,非常意外的是,在拜耳法应用中, 在交联之后可显著提高葡聚糖的活性。 Thus, when the crosslinked polysaccharide true for mining applications, such as, for example, in U.S. Patent No. 4,339,331 and .5,049,612, it is very unexpected that, in the Bayer process applications, after crosslinking can significantly increase the activity of dextran . 此外,交联多糖具有高达或至少50%的性能改善或增加多糖的最大有效剂量之能力是意外和新颖的。 Further, the crosslinked polysaccharide having improved or at least up to 50% increase in performance or ability of a polysaccharide of the maximum effective dose is unexpected and novel. 在至少一个实施方案中,通常的交联试剂/多糖的质量比率可在但不限于约〇与0.2之间变化。 In at least one embodiment, the mass ratio of cross-linking agents usually / polysaccharide may vary between, but not limited to square and about 0.2. 具体地,对于表氯醇作为交联试剂, 比率可在但不限于1与0.1之间,优选地在0.005与0.08之间变化。 In particular, epichlorohydrin as a crosslinking agent, but are not limited to, the ratio may be between 1 and 0.1, preferably between 0.005 and 0.08 change. 如通过在原始溶液粘度之上的至少10%的溶液粘度增加所测量的,完成了适当的交联。 As measured by solution viscosity on an original solution viscosity of at least 10% increase in the measured completed appropriate crosslinking.

[0035] 在至少一个实施方案中,将组合物添加到在所述三水合氧化铝生产工艺的三水合物分级回路中的料液中。 [0035] In at least one embodiment, the composition is added to the feed solution in the circuit trihydrate classification of alumina trihydrate in the production process. 可将组合物在拜耳法中的一个或更多个位置处添加到所述料液中,其中发生固_液分尚。 The composition may be added at one or more of the Bayer process to position the feed solution, wherein the liquid separation still occurs _ solid.

[0036] 在至少一个实施方案中,可将组合物在拜耳法中的一个或更多个位置处添加到所述料液中,其中其在所述方法中抑制一个或更多个三水合氧化铝晶体的成核速度。 [0036] In at least one embodiment, may be added at a composition of the Bayer process or more locations to the feed solution, wherein one or more of which inhibits trihydrate in the method rate of nucleation of aluminum crystals.

[0037] 在至少一个实施方案中,可将所述组合物在拜耳法中的一个或更多个位置处添加到所述料液中,其中其在所述方法中降低结垢速度。 [0037] In at least one embodiment, may be added to the composition at a Bayer or more locations to the feed solution, where it reduces the fouling rate in the process.

[0038] 在至少一个实施方案中,可将所述组合物在拜耳法中的一个或更多个位置处添加到所述料液中,其中其在所述方法中促进赤泥澄清。 [0038] In at least one embodiment, may be added to the composition at a Bayer or more locations to the feed solution, wherein the red mud which promotes the clarification process.

[0039] 在至少一个实施方案中,可将所述组合物与美国专利8,252,266所公开的组合物和方法的任意一个组合来添加或者根据其来添加。 [0039] In at least one embodiment, the composition may be in any of U.S. Patent No. 8,252,266 disclosed compositions and methods, or a combination to be added in accordance with its added. 实施例 Example

[0040] 通过参考以下实施例可更好地理解前述内容,所述实施例是为了说明的目的呈现而并不旨在限制本发明的范围。 [0040] reference to the following embodiments may be better understood from the foregoing, the examples are presented for purposes of illustration and are not intended to limit the scope of the present invention.

[0041] 实施例1: [0041] Example 1:

[0042] 将50克纤维素(溶解木浆,巴伊亚浆(bahia pulp) ,Solucell 350,在使用Imm筛网的Retsch研磨机上碎裂)加入装备有双螺旋形式的高架搅拌器的1500ml圆柱形反应烧瓶中。 [0042] 50 g of cellulose (dissolving pulp, pulp Bahia (bahia pulp), Solucell 350, in the use of fragmentation Imm screen Retsch grinder) which was equipped with overhead stirrer double helix form of a cylindrical 1500ml type reaction flask. 将纤维素混悬于800克2-甲基-2-丁醇中并封闭反应烧瓶。 Cellulose suspended in 800 g tert-amyl alcohol and closed reaction flask. 将混悬液保持在环境温度下并用底部氮气吹扫脱氧,同时在250rpm下旋转搅拌器。 The suspension was kept at ambient temperature and deoxygenated with a nitrogen purge at the bottom, while rotating stirrer at 250rpm. 将底部氮气吹扫保持30分钟。 The bottom was purged with nitrogen for 30 minutes. 此时, 将底部氮气吹扫改为顶部氮气覆盖并且将69.1克25%的氢氧化钠溶液添加到混悬的纤维素纤维浆料中。 At this time, top to bottom was purged with nitrogen and a nitrogen blanket is added 69.1 g of 25% sodium hydroxide solution to the cellulosic fiber slurry in suspension. 继续搅拌纤维素浆料并且经过60分钟时间将温度从环境温度逐渐升高到80 °C。 Cellulose pulp and stirring was continued over 60 minutes The temperature was gradually increased from ambient temperature to 80 ° C. 将69g缩水甘油(Aldrich)以Iml/分钟的进料速度添加到搅拌的碱化纤维素浆料中。 The 69g of glycidol (Aldrich) at a feed rate of Iml / min is added to the stirred slurry of the alkalized cellulose. 将浆料的温度保持在80°C下并通过加热或冷却来控制。 The temperature of the slurry is maintained at 80 ° C for and controlled by heating or cooling. 将混合物在温度下保持另外的20分钟。 The mixture was further kept at the temperature for 20 minutes. 此时,将14克乙烯基磺酸钠(Aldrich)以Iml/分钟的进料速度添加到升温(80°C)并搅拌的混合物中。 At this time, 14 g sodium vinyl sulfonate (Aldrich) was added to a warmed (80 ° C) at a feed rate of Iml / min and the mixture was stirred. 在完成添加之后,将混合物在80 °C下搅拌另外的60分钟。 And the mixture was stirred for an additional 60 minutes at 80 ° C for after the completion of the addition. 在此时取得的产物样品是完全水溶性的。 Samples were acquired at the time the product is completely water-soluble. 以酚酞(粉红至澄清)为指示标准用乙酸(约29.5g)来中和碱化的纤维素醚的浆化混合物。 Phenolphthalein (until clear pink) to the mixture and basified slurried cellulose ether with acetic acid (approximately 29.5 g of) indicative of a standard. 通过过滤从反应浆料中作为湿润滤饼来分离粗制2,3_二羟丙基-乙基磺化纤维素。 By filtration from the reaction slurry is isolated as a moist press cake of crude 2,3_-dihydroxypropyl - sulfonated ethyl cellulose. 将滤饼在两步过程中干燥。 The filter cake was dried in a two step process. 在即时通风、干燥烘箱中在60°C下经过60分钟时间移除大多数有机挥发物。 Instant ventilated drying oven after 60 minutes most of the organic volatiles were removed at 60 ° C. 在〇. OlmmHg下并且温度不超过25°C下经过46小时时间蒸发在粗制纤维素醚中的残留水。 In the square. OlmmHg and at a temperature not exceeding 25 ° C at 46 hours elapsed time in the crude cellulose ether is evaporated residual water. 分离150克粗制干燥产物,其包含24 %的乙酸钠和76 %的2,3-二羟丙基-乙基磺化纤维素。 150 g of crude dried product was isolated, which contained 24% of sodium acetate and 76% of 2,3-dihydroxypropyl - sulfonated ethyl cellulose. 2%的粗制、干燥纤维素醚溶液的粘度为36CpS(30rpm,22°C,转子LS62)。 Crude 2%, the viscosity of the cellulose ether solution is dried 36CpS (30rpm, 22 ° C, rotor LS62).

[0043] 实施例2: [0043] Example 2:

[0044] 将43克纤维素(溶解木浆、Toba Pulp Lestari,Tobacell EUC 94,在使用Imm筛网的Retsch研磨机上碎裂)加入装备有双螺旋形式的高架搅拌器的1500ml圆柱形反应烧瓶中。 1500ml cylindrical reaction flask [0044] A 43 g of cellulose (dissolving pulp, Toba Pulp Lestari, Tobacell EUC 94, in the use of fragmentation Imm screen Retsch grinder) which was equipped with an overhead stirrer in the form of a double helix of . 将纤维素混悬于800克2-甲基-2-丁醇中并封闭反应烧瓶。 Cellulose suspended in 800 g tert-amyl alcohol and closed reaction flask. 将混悬液保持在环境温度下并用底部氮气吹扫脱氧,同时在250rpm下旋转搅拌器。 The suspension was kept at ambient temperature and deoxygenated with a nitrogen purge at the bottom, while rotating stirrer at 250rpm. 将底部氮气吹扫保持30分钟。 The bottom was purged with nitrogen for 30 minutes. 此时, 将底部氮气吹扫改为顶部氮气覆盖并且将59.5克25%的氢氧化钠溶液添加到混悬的纤维素纤维浆料中。 At this time, top to bottom was purged with nitrogen and a nitrogen blanket is added 59.5 g of 25% sodium hydroxide solution to the cellulosic fiber slurry in suspension. 继续搅拌纤维素浆料并且经过60分钟时间将温度从环境温度逐渐升高到80 °C。 Cellulose pulp and stirring was continued over 60 minutes The temperature was gradually increased from ambient temperature to 80 ° C. 将59g缩水甘油(Aldrich)以Iml/分钟的进料速度添加到搅拌的碱化纤维素浆料中。 The 59g of glycidol (Aldrich) at a feed rate of Iml / min is added to the stirred slurry of the alkalized cellulose. 在完成添加之后,将混合物在80°C下搅拌另外的60分钟。 And the mixture was stirred for an additional 60 minutes at 80 ° C for after the completion of the addition. 在此时取得的产物样品几乎不含混悬的固体。 In the sample of the product acquired at the time almost free of suspended solids. 以酚酞(粉红至澄清)为指示标准用乙酸(约22.6g)来中和碱化的纤维素醚的浆化混合物。 Phenolphthalein (until clear pink) to the mixture and basified slurried cellulose ether with acetic acid (approximately 22.6 g of) indicative of a standard. 通过过滤从反应浆料中作为湿润滤饼来分离粗制2,3_二羟丙基纤维素。 By filtration from the reaction slurry is isolated as a moist press cake of crude 2,3_-dihydroxypropyl cellulose. 将滤饼在两步步骤过程中干燥。 The filter cake was dried in a two step process. 在即时通风、干燥烘箱中在60°C下经过60分钟时间移除大多数有机挥发物。 Instant ventilated drying oven after 60 minutes most of the organic volatiles were removed at 60 ° C. 在0.0 ImmHg下并且温度不超过25 °C下经过16小时时间蒸发在粗制纤维素醚中的残留水。 0.0 ImmHg and at a temperature not exceeding 25 ° C after 16 hours under the crude cellulose ether is evaporated residual water. 分离117.3克粗制干燥产物,其包含26%的乙酸钠和74%的2,3_二羟丙基纤维素。 117.3 g of crude product was separated and dried, containing 26% of sodium acetate and 74% 2,3_-dihydroxypropyl cellulose. 2%的粗制、干燥纤维素醚料液的粘度为36cps (30rpm,22°C,转子LS62)。 Crude 2%, the viscosity of the cellulose ether sulfate feed solution was 36cps (30rpm, 22 ° C, rotor LS62).

[0045] 实施例3: [0045] Example 3:

[0046] 将8g如实施例1中所制备的并且粘度为35cps (2%,30rpm,23°C,转子LS62)的粗制2,3-二羟丙基-乙基磺化纤维素溶解于92g水中。 [0046] The viscosity and 8g prepared as in Example 1 to 35cps (2%, 30rpm, 23 ° C, rotor LS62) of crude 2,3-dihydroxypropyl - sulfonated cellulose was dissolved in ethyl 92g water. 将1.02g域如下表所示的)50 %的NaOH溶液添加到混合物中并用高架笼状叶轮在2000rpm下剧烈搅拌所得溶液直到混合物均质/均相为止,约2分钟。 A) 50% NaOH was added 1.02g field as shown below in Table elevated to the mixture and with an impeller cage resulting solution was vigorously stirred at 2000rpm until the mixture was homogeneous / homogeneous, about 2 minutes. 将0.527g (或如下表所示的)表氯醇(Fluka)添加到混合物中并用高架笼状叶轮在2000rpm下再次剧烈搅拌所得溶液直到混合物均质为止,约5分钟。 The 0.527 g (or as shown in the table) of epichlorohydrin (Fluka) was added to the mixture and the basket with an overhead impeller was again stirred vigorously at 2000rpm until the resulting mixture is homogenized solution, for about 5 minutes. 使混合物静止过夜16小时以形成连续的交联凝胶。 The mixture was allowed to stand overnight for 16 hours to form a continuous crosslinked gel. 将反应粗品稀释至2%,以酚酞为指示标准用乙酸来中和并用非氧化性杀生物剂例如Kathon⑩.来抑制微生物降解。 The reaction crude was diluted to 2% phenolphthalein as indicated by standard acid and neutralized with a biocide e.g. Kathon⑩ nonoxidative. To inhibit microbial degradation. 如此制备的交联2,3-二羟丙基-乙基磺化纤维素溶液适于作为拜耳法中的三水合氧化铝的促凝剂和絮凝剂。 Crosslinking the thus prepared 2,3-dihydroxypropyl - ethyl cellulose solutions are suitable as sulfonating alumina trihydrate in the Bayer process coagulants and flocculants.

[0047] 表1: [0047] Table 1:

[0048] [0048]

Figure CN105073642BD00081

[0049] EPI表氯醇 [0049] EPI epichlorohydrin

[0050] AGU 2,3-二羟丙基-乙基磺化纤维素的无水葡萄糖单体单元 [0050] AGU 2,3- dihydroxypropyl - sulfonated ethyl cellulose anhydroglucose monomeric units

[0051] NaOH氢氧化钠 [0051] NaOH sodium hydroxide

[0052] 详细地研究了乙基磺化二羟丙基纤维素与乙基磺化二羟丙基纤维素、二羟丙基纤维素或羟乙基纤维素的交联反应。 [0052] studied the sulfonated ethyl cellulose with dihydroxypropyl hydroxypropyl cellulose ethyl disulfonated detail, the crosslinking reaction of two hydroxypropyl cellulose or hydroxyethyl cellulose. 在交联剂与二羟丙基纤维素或羟乙基纤维素之间的反应过程中学到的见解可直接转移到乙基磺化二羟丙基纤维素的交联。 During the reaction between the crosslinker and the two middle school hydroxypropyl cellulose or hydroxyethyl cellulose may be directly transferred to the insight into the crosslinked sulfonated ethyl dihydroxypropyl cellulose. 相关反应的表格式总结在以下表2和表3中示出。 Tabular related reactions are summarized in the following Table 2 and Table 3 shows.

[0053] 表2: [0053] Table 2:

Figure CN105073642BD00091

Figure CN105073642BD00101

Figure CN105073642BD00111

[0058] [0058]

Figure CN105073642BD00121

[0059] 实施例的结果如下: [0059] The results of the examples are as follows:

[0060] I.二羟丙基纤维素醚的DS (取代度,在纤维素链中的每个单体葡萄糖单元中二羟丙基数)为0.5至3.0。 [0060] I. dihydroxypropyl cellulose ether DS (degree of substitution, the number of two per monomer hydroxypropyl cellulose glucose unit chain) is 0.5 to 3.0.

[0061] 2.二羟丙基纤维素醚的优选DS为1.5至2.5。 [0061] Preferably DS 2. dihydroxypropyl cellulose ether is 1.5 to 2.5.

[0062] 3.除了1.5 to 2.5的DS之外,二羟丙基纤维素醚还可具有大于或等于1的MS (多取代度,在纤维素链中附加在单体葡萄糖单元上的每个单一氢氧化物中的二羟丙基的平均数量)。 [0062] 3. In addition to the DS of 1.5 to 2.5, dihydroxypropyl cellulose ether having MS may be greater than or equal to 1 (multiple degrees of substitution, attached to the monomer unit in the cellulose chain of glucose each the average number of single hydroxides dihydroxypropyl).

[0063] 4.二羟丙基纤维素醚具有阴离子取代基。 [0063] 4. dihydroxypropyl cellulose ether has an anionic substituent.

[0064] 5.二羟丙基纤维素醚具有阴离子取代基,阴离子组分的DS大于0且小于0.5。 [0064] The hydroxypropyl cellulose ether having two anionic substituent, DS anionic component is greater than 0 and less than 0.5.

[0065] 6.在二羟丙基纤维素醚上优选的阴离子取代基是乙基磺酸盐基团。 [0065] 6. dihydroxypropyl cellulose ether in preferred anionic substituent group is an ethyl sulfonate groups.

[0066] 7.二羟丙基乙基磺化纤维素在均质或异质条件下进行交联。 [0066] 7. ethyl dihydroxypropyl cellulose, sulfonated crosslinked under homogeneous or heterogeneous conditions.

[0067] 8.在各个二羟丙基乙基磺化纤维素醚之间的交联是共价性质的。 [0067] 8. The two cross-linking between the respective sulfonated hydroxypropyl ethyl cellulose ether is a covalent nature.

[0068] 9.二羟丙基乙基磺化纤维素醚的交联具有增加其分子量和其溶液粘度的作用。 [0068] 9. The crosslinked sulfonated ethyl dihydroxypropyl cellulose ether having an increased molecular weight and solution viscosity effects.

[0069] 10.二羟丙基乙基磺化纤维素在交联之前在30rpm,20°C和2%活性物含量下的布氏粘度为1〇〇口8至100〇口8,而在交联之后在30印111,20<€和2%下的布氏粘度为200〇口8至3000cps〇 [0069] 10. A sulfonated cellulose, ethyl dihydroxypropyl before crosslinking Brookfield viscosity at 30rpm, 20 ° C and 2% active content is 8 to 100〇 1〇〇 port opening 8, and in after crosslinking printing 30 111,20 <€ and a Brookfield viscosity of 2% to 8 200〇 port 3000cps〇

[0070] 11.交联二羟丙基乙基磺化纤维素能够在拜耳法中增强三水合氧化铝固体从富集过程料液中的絮凝。 [0070] 11. The crosslinked sulfonated dihydroxypropyl ethyl cellulose to enhance alumina trihydrate solids from the feed liquid in the enrichment process of flocculation in the Bayer process.

[0071] 虽然可以许多不同形式实施本发明,但是在本文中详细地描述了本发明的具体优选实施方案。 [0071] While the embodiment of the present invention may be in many different forms, but are described herein specific preferred embodiments of the present invention in detail. 本公开内容是本发明原理的举例说明而不旨在将本发明限制于所说明的特定实施方案中。 The present disclosure is illustrative of the principles of the present invention is not intended to specific embodiments of the present invention be limited to the illustrated. 本文所提及的所有专利、专利申请、科学论文和任何其他参考资料均通过引用以其整体并入。 All patents, patent applications, scientific papers, and any other references mentioned herein are incorporated by reference in their entirety. 此外,本发明涵盖本文所述的和/或本文所并入的多个实施方案的一些或全部的任何可能组合。 Furthermore, any possible combination of some or all of the various embodiments of the present invention encompasses herein and / or incorporated herein. 此外,本发明还涵盖明确地排除在本文所述的和/或本文所并入的多个实施方案的任意一个或一些之外的任何可能组合。 Further, the present invention also encompasses specifically excluded from any of a number of embodiments described herein and / or incorporated herein, in addition to some or any possible combination.

[0072] 上述公开内容旨在说明而非穷举。 [0072] The above disclosure is intended to be illustrative and not exhaustive. 对于本领域普通技术人员而言,该描述暗含许多变化和替代。 For those of ordinary skill in the art, which implies many variations and alternatives described. 所有这些替代和变化均旨在包括在权利要求的范围内,其中术语“包括”意指“包括但不限于”。 All these alternatives and variations are intended to be included within the scope of the claims where the term "comprising" means "including but not limited to." 本领域技术人员将承认本文所述的具体实施方案的其他等同方案,这些等同方案也旨在被权利要求所涵盖。 Those skilled in the art will recognize other equivalents to the specific embodiments described herein embodiments, these equivalents are also intended to be encompassed by the claims.

[0073] 应理解,本文所公开的所有范围和参数均涵盖其中所包含的任何和所有子范围, 以及在端点之间的每个数字。 [0073] It should be understood that all ranges and parameters are disclosed herein encompass any and all subranges subsumed therein, and every number between the end points. 例如,所规定的范围“1至10”应被认为包括最小值1与最大值10之间(和包括1和10在内)的任何和所有子范围,即,以最小值1或更大(例如1至6.1)开始并以最大值10或更小(例如,2.3至9.4,3至8,4至7)结束以及最后被认为该范围内所包含的每个数字1、2、3、4、5、6、7、8、9、10的所有子范围。 For example, a predetermined range of "1 to 10" should be considered to include (and including 1 and 10 inclusive) of any and all sub-ranges between the minimum value of 1 and the maximum value 10, i.e., the minimum value of 1 or more ( for example 1 to 6.1) at the start and maximum value of 10 or less (e.g., 2.3 to 9.4,3 to 8,4 to 7) and the end of the last numbers within that range that each contained 1,2,3,4 , 8, 9, of all sub-ranges. 除非另有说明,否则本文的所有百分比、比率和比例均按重量计。 Unless otherwise indicated, all percentages, ratios and proportions herein are by weight.

[0074] 至此完成了本发明的优选和替代实施方案的描述。 [0074] This completes the description of the preferred and alternative embodiments of the present invention. 本领域技术人员应当能够认识至IJ,所附的权利要求书旨在涵盖其他等同于本文所述的具体实施方案的等同实施方案。 Those skilled in the art should be able to recognize IJ, the appended claims are intended to cover other equivalents to the specific embodiments described herein equivalent embodiments.

Claims (8)

  1. 1. 一种利用拜耳法来生产氧化铝的方法,所述方法包括向所述拜耳法的料液或浆料中添加包含一种或更多种乙基磺化交联多糖的组合物的步骤,其中所述交联多糖包括通过使二羟丙基纤维素与交联剂进行交联以形成交联分子所制成的反应产物,和其中所述交联剂为表氯醇, 其中所述交联多糖是二羟丙基纤维素并且纤维素链中每个单体葡萄糖单元中的二羟丙基数为0.5至3.0,和其中二羟丙基乙基磺化纤维素在交联之前在30rpm、20 °C和2 %活性物含量下的布氏粘度为IOcps至lOOcps;而在交联之后在30rpm、20°C和2%活性物含量下的布氏粘度为200cps 至3000cps。 1. A process for production of alumina using the Bayer method, the method comprising the step of adding ethyl comprising one or more sulfonated crosslinked polysaccharide composition or slurry material to the Bayer process wherein the crosslinked polysaccharide comprises hydroxypropyl cellulose with a dicarboxylic by crosslinking the crosslinking agent to form a reaction product made by crosslinking molecules, and wherein the crosslinker is epichlorohydrin, where the crosslinked polysaccharide is hydroxypropyl cellulose and the two number-dihydroxypropyl cellulose chain monomer per glucose unit is 0.5 to 3.0, and wherein the sulfonated cellulose, ethyl dihydroxypropyl before crosslinking at 30rpm , 20 ° C and a Brookfield viscosity at 2% of active content IOcps to lOOcps; whereas after crosslinking Brookfield viscosity at 30rpm, 20 ° C and 2% active content is 200cps to 3000cps.
  2. 2. 根据权利要求1所述的方法,其中所述交联多糖已与足够量的乙烯基磺酸钠或氯代乙酸钠反应以赋予所述多糖以一个或更多个阴离子取代区域。 2. The method according to claim 1, wherein said polysaccharide is crosslinked with a sufficient amount of sodium or sodium vinyl chloroacetate reacted to impart the polysaccharide is substituted with one or more anionic region.
  3. 3. 根据权利要求1所述的方法,其中所述二羟丙基纤维素是纤维素与3-氯-1,2-丙二醇反应的反应产物。 3. The method according to claim 1, wherein said reaction product dihydroxypropyl cellulose is a cellulose-propanediol with epichlorohydrin.
  4. 4. 根据权利要求1所述的方法,其中将所述组合物在一个或更多个位置处添加到所述料液中从而抑制所述拜耳法中一个或更多个三水合氧化铝晶体的成核速度。 4. The method according to claim 1, wherein the composition is added at one or more locations to the liquor in the Bayer process to suppress one or more of alumina trihydrate crystals nucleation rate.
  5. 5. 根据权利要求1所述的方法,其中将所述组合物在一个或更多个位置处添加到所述料液中从而降低所述拜耳法中的结垢速度。 The method according to claim 1, wherein the composition is added to at one or more locations in the liquor thereby reducing the fouling rate in the Bayer process.
  6. 6. 根据权利要求1所述的方法,其中将所述组合物在一个或更多个位置处添加到所述料液中以促进所述拜耳法中的赤泥澄清。 6. The method according to claim 1, wherein the composition is added to the clarification of red mud feed liquid to facilitate the Bayer process at one or more positions.
  7. 7. 根据权利要求1所述的方法,其中所述组合物添加通过将所述组合物添加到所述拜耳法的所述料液中提高了从三水合氧化铝工艺中分离三水合氧化铝的产率。 7. The method according to claim 1, wherein said composition is added to the composition is added to the liquor in the Bayer process trihydrate improves the separation process from the alumina trihydrate by Yield.
  8. 8. 根据权利要求1所述的方法,其中所述交联多糖还包括通过使硬葡聚糖、葡聚糖、硬葡聚糖和葡聚糖的组合、硬葡聚糖和二羟丙基纤维素的组合、葡聚糖和二羟丙基纤维素的组合、以及硬葡聚糖和葡聚糖和二羟丙基纤维素的组合之一与交联剂交联以形成交联分子所制成的反应产物。 8. The method according to claim 1, wherein the crosslinked polysaccharide by further comprising scleroglucan, dextran combinations, scleroglucan and dextran, scleroglucan and dihydroxypropyl a combination of cellulose, dihydroxypropyl cellulose, and dextran, as well as a combination of one and two scleroglucan dextran and hydroxypropyl cellulose with a crosslinking agent to form a crosslinked molecules made from the reaction product.
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