CN1082058C - Co-polymer of sulfonate, the prepn. method and use thereof - Google Patents

Co-polymer of sulfonate, the prepn. method and use thereof Download PDF

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CN1082058C
CN1082058C CN 97103642 CN97103642A CN1082058C CN 1082058 C CN1082058 C CN 1082058C CN 97103642 CN97103642 CN 97103642 CN 97103642 A CN97103642 A CN 97103642A CN 1082058 C CN1082058 C CN 1082058C
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polymer
sulfonate
prepn
method
use
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CN1161347A (en )
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吴文元
唐荣趾
贺靛
魏槟
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北京天龙水处理技术公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides
    • C08F220/58Amides containing oxygen in addition to the carbonamido oxygen

Abstract

本发明涉及磺酸盐共聚物及其制备方法和用途。 The present invention relates to sulfonate copolymers and preparation method and use. 本发明目的在于提供一种不含磷的磺酸盐共聚物作为水处理剂,尤其对恶劣水质如高碱、高硬度、高PH值的水分散阻垢和缓蚀、絮凝,克服已有技术造成“三废”问题。 Object of the present invention to provide a copolymer salt of phosphorous as water treatment agent, especially poor water quality such as high alkaline, high hardness, high PH value of the water dispersion of scale and corrosion inhibition, flocculation, caused by the prior art to overcome "waste" problem. 本发明由单体AMPS与单体B、单体C,以水为溶剂,在引发剂作用下,在反应釜内温度为20-125℃下,聚合反应30-300分钟,生成多元磺酸盐共聚物。 The present invention consists of AMPS monomers and monomers B, from monomers C, from water as a solvent, in the role of initiator, the temperature in the reactor is at 20-125 deg.] C, the polymerization reaction was 30-300 minutes to produce polyhydric sulfonate copolymer. 该产物用做处理水的分散阻垢、缓蚀、絮凝剂,阻垢效率达85%,该制备工艺简单,反应一步完成,大大降低成本。 The product was used as a dispersion treatment water scale, corrosion, flocculants, scale up to 85% efficiency, the preparation process is simple, one step reaction, greatly reducing costs.

Description

磺酸盐共聚物及其制备方法和用途 Sulfonate copolymer and preparation and use

本发明涉及一种水处理剂和制备方法,特别是用磺酸盐共聚物作为水处理剂及其制备方法和用途。 The present invention relates to a water treatment agent and methods of preparation, in particular a copolymer with sulfonate as water treatment agent and its preparation and uses.

目前在工业上已用含磺酸盐共聚物作为阻垢分散剂,如文献1,“含磺酸盐共聚物作为阻垢分散剂的技术现状”(工业水处理,1993,V01.13.№4)中所述的,这类含磺酸盐共聚物阻垢作用不受水中是否存在金属离子的影响,尤其对P、S、Ca、Ba、Mg、(OH)2、CaCO3等盐垢有良好抑制作用,药力持久,不易结胶等优点,它可分为五大类; Currently in the industry has a sulfonate-containing copolymer as a scale dispersant, such as Document 1, "sulfonate-containing copolymer as a state of the art DISPERSOR" (Industrial Water Treatment, 1993, V01.13.№ 4) was used, whether the presence of such metal ions sulfonate-containing copolymer is not water scale inhibition, especially P, S, Ca, Ba, Mg, (OH) 2, CaCO3 and other salts with a scale good inhibitory drug lasting, easy gumming, etc., which can be divided into five categories;

其中:AA:丙烯酸,MA:马来酸(酐);SS:苯乙烯磺酸AMPS:2-丙烯酰胺基-2-甲基丙烷磺酸-1;AM:丙烯酸胺AMPP:2-丙烯酰胺基-2-甲基丙烷磷酸HAPS:2-羟基-3-烯丙氧基-1-丙基磺酸ABS:烯丙氧基苯磺酸;MBSN异戊二烯磺酸盐 Wherein: AA: acrylic acid, MA: maleic acid (anhydride); SS: styrene sulfonate AMPS: 2- acrylamido-2-methylpropanesulfonic acid -1; AM: acrylamide AMPP: 2- acrylamido- 2-methylpropanesulfonic acid HAPS: 2- hydroxy-3-allyloxy-1-propanesulfonic ABS: allyloxybenzenesulfonic acid; MBSN isoprene sulfonate

HPA:丙烯酸羟丙酯五类磺酸盐单体中,除双烯烃类外,国外均已成批生产。 HPA: hydroxypropyl acrylate five salt monomer, in addition to the olefinic double abroad have been mass-produced. 其中,乙烯磺酸、丙烯磺酸,由于其本身不易进行游离基聚合,因而在水处理工业中的使用受到限制;苯乙烯磺酸因其磺酸对对位的乙烯有诱导作用,使之处于较高的活性,故比其它单体易聚合,且热稳定性好,但制造过程复杂、价格高,单位重量所含的磺基少;磺化甲基、乙基丙烯酸与苯乙烯相比,虽成本较低,但易于水解,不稳定,从而也限制了它的使用;AMPS价格适中,易于制造是最受欢迎的单体。 Wherein, vinylsulfonic acid, acrylic acid, because of its own is not easy to carry out radical polymerization, and thus in the water treatment industry is limited; styrene sulfonic acid has its effect on the induction of ethylene bits, so that in higher activity, it is easy than other monomers, and good thermal stability, but the manufacturing process is complicated, expensive, low unit weight contained sulfo; sulfonated methyl, ethyl acrylate, compared with styrene, although low cost, but susceptible to hydrolysis and unstable, thus limiting its use; AMPS affordable, easy to manufacture is the most popular single. HAPS、ABS及MBSN是新开发的磺酸(盐),但它阻垢还不理想。 HAPS, ABS and MBSN is a newly developed sulfonic acid (salt), but its scale is not ideal.

随后世界上开发磺化苯乙烯-马来酐共聚物(SSMA)作为水处理剂,阻垢效果从文献2,“磺化苯乙烯-马来酐共聚物的合成及其阻垢性能研究”(工业水处理,1994,V01.14.№ 5)文中表明:在Ca+2浓度300×10-6以下,PH=8.5以下具有较好的CaCO3垢的阻垢性能,或者需与有机磷酸、锌盐等共同使用阻垢效果更好。 Subsequently developed world sulfonated styrene - maleic anhydride copolymer (SSMA) as a water treatment agent, from the scale inhibition Document 2 "sulfonated styrene - maleic anhydride copolymers and their scale inhibition" ( industrial water treatment, 1994, V01.14.№ 5) indicates that the text: the Ca + 2 concentration of 300 × 10-6 or less, PH = 8.5 or less has good scale inhibition performance CaCO3 scale, or with an organic acid required, zinc salt and other commonly used scale better. SSMA的合成有两种方法,一种是苯乙烯(ST)单体先磺化,然后用磺化苯乙烯与马来酐(MA)进行共聚。 There are two methods of synthesis of SSMA a styrene (ST) to a sulfonated monomer, and copolymerized with maleic anhydride (MA) with sulfonated styrene. 另一种方法是先制取苯乙烯-马来酐共聚物(SMA),然后将共聚物磺化。 Another method of preparation is to styrene - maleic anhydride copolymer (SMA), and then the sulfonated copolymer. 具体工艺如下:先合成SMA(苯乙烯-马来酐共聚物)采用BPO为引发剂,丁酮为溶剂,在回流温度下进行共聚反应制备苯乙烯∶马来酐=1∶1(分子比)共聚物,其聚合——反应温度80℃,单体浓度20%,两单体分子比为1∶1,BPO用量5%,反应时间4小时。 Specific processes are as follows: First Synthesis of the SMA (styrene - maleic anhydride copolymer) using BPO as the initiator, the solvent is methyl ethyl ketone, prepared styrene copolymer was reacted at reflux temperature: maleic anhydride = 1:1 (mole ratio) copolymer, polymerization - the reaction temperature is 80 ℃, the monomer concentration of 20%, two monomer molecular ratio of 1:1, BPO amount of 5%, a reaction time of 4 hours. 然后进行SMA的磺化共聚反应结束后,向共聚物溶液中滴加SO3-HCCI3混合液,加入HCCI3是为了稀释SO3,其磺化——反应温度10℃CO3∶ST=1∶1(分子比)反应时间为1.5小时。 Then sulfonation of SMA copolymerization After completion of the reaction, the mixed solution was added dropwise SO3-HCCI3 copolymer solution, is added to dilute the HCCI3 of SO3, sulfonation - a reaction temperature of 10 ℃ CO3:ST = 1:1 (mole ratio ) the reaction time was 1.5 hours. 磺化结束后加入沉淀剂,使产物析出,过滤,滤饼在真空烘箱中干燥,得粉块状SSMA。 After the sulfonating agent is added to precipitate the product precipitated, was filtered, the filter cake was dried in a vacuum oven to give the bulk powder SSMA.

前一种方法不能用苯乙烯直接磺化,通常是先将2-卤代乙苯磺化后再用碱脱去卤化氢,制得苯乙烯磺酸盐再与马来酸酐共聚,因而过程复杂,成本高。 The former method can not direct sulfonation of styrene, ethylbenzene is usually first 2-halo-sulfonated then dehydrohalogenation with a base to prepare a re-copolymerizing styrene sulfonate with maleic anhydride, which process is complicated ,high cost.

后一种制备方法中由于采用了丁酮作溶剂原料价格贵,而增加成本,另外在生产过程中还采用有强烈刺激气味的丙烯酸酯类原料,故对生产工人及周围环境均受影响;并且生产还要排放废液造成对环境污染。 The latter preparation method using butanone as solvent since expensive raw materials, and an increase in cost, the production process in addition also be employed to stimulate a strong odor of acrylic material, so that production workers are affected and surrounding environment; and also emissions from the production of waste pollute the environment.

另外在<精细石油化工>1991(6)33-38中报道“顺丁烯二酸共聚物钡锶离子稳定剂”文章中报道以顺酐为主要原料合成离子稳定剂用于油田水处理,但未有采用AMPS用原料。 Also in & lt; Petrochemicals & gt; 1991 (6) 33-38 reported "maleic acid copolymer stabilizer, barium strontium" article reported to maleic anhydride as the main materials used in oil field water treatment ionic stabilizer but using AMPS No raw material.

本发明的目的在于克服上述已有技术的缺点和不足,提供一种新型不含磷的磺酸盐共聚物水处理剂,用在高硬度、高碱度、高PH值的恶劣水质情况下的分散阻垢和缓蚀、絮凝。 Object of the present invention is to overcome the above disadvantages and shortcomings of the prior art, providing a novel sulphonate copolymer containing no phosphorus, in harsh water conditions with high hardness, high alkalinity, high PH value of disperse scale and corrosion inhibition, flocculation.

目的之二在于解决已有技术造成“三废”问题。 Another object of the prior art to solve the resulting "waste" problem.

目的之三在于降低成本,反应不需浓缩工序,达到反应一步完成,提高聚合物的回收率,并且制备方法简单。 The object is to reduce the cost of three, without concentrating the reaction step, to complete the reaction step, increase the recovery rate of the polymer, and preparation method is simple.

本发明的目的是这样实现的:本发明提供的多元磺酸盐共聚物其结构为: Object of the present invention is implemented as follows: the present invention provides a copolymer of polycarboxylic acid salt having the structure: 其中m=10-100;p=10-100;k=0-3;分子量为1000-10000;本发明提供一种由单体A:2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS)和单体B,还可加入单体C,它以水为溶剂,在加入引发剂情况下聚合生成多元磺酸盐共聚物。 Where m = 10-100; p = 10-100; k = 0-3; molecular weight 1000-10000; the present invention provides a monomer A: 2- acrylamido-2-methylpropanesulfonic acid (AMPS ) and monomers B, from the monomers may be added to C, which water as a solvent, in the case of addition of the polymerization initiator generating sulfonate copolymer polyol.

其中单体B:有机酸酐,单体C可以是丙烯酸、丙烯腈、丙烯酸酯,引发剂可以是高锰酸钾、次氯酸钠、过氧化氢、过硫酸盐;有机酸酐最好为:顺丁烯二酸酐;单体A(AMPS)可和一个单体B聚合,还可以和一个或一个以上单体C聚合生成多元磺酸盐共聚物。 Wherein monomer B: Organic acid anhydride monomer C may be acrylic acid, acrylonitrile, acrylate, initiator may be potassium permanganate, sodium hypochlorite, hydrogen peroxide, persulfates; preferably organic acid anhydride: maleic anhydrides; monomer a (AMPS) can be polymerized and a monomer B, may also be one or more monomers and polymerization of polycarboxylic acid salt copolymer C.

本发明提供制备二元磺酸盐共聚物的方法是选用单体A与单体B与引发剂,按A∶B∶引发剂(重量比)=5-50∶10-90∶1-6配料,其反应为: The present invention provides a method of preparing two yuan sulfonate copolymer is optional monomers A and B monomers and initiator, initiator according A:B: (weight ratio) = 5-50:10-90:1-6 Ingredients , the reaction is: 其生成三元磺酸盐共聚物是单体A与单体B、C和引发剂,按A∶B∶C∶引发剂(重量比)=5-30∶10-80∶50∶1-10配料,其反应式为: Generating three yuan sulfonate copolymer is a monomer A and a monomer B, C and initiator, initiator according A:B:C: (weight ratio) = 5-30:10-80:50:1-10 ingredients, the reaction is: 其中n=10-100,m=10-100,p=10-100,分子量为1000-10000;将上述原料溶液混合配好,送入反应釜中,进行聚合反应,其反应温度均为-20-125℃聚合反应时间30-300分钟,按通常聚合反应步骤进行,即可制备出多元的磺酸盐共聚物。 Where n = 10-100, m = 10-100, p = 10-100, molecular weight 1000-10000; and mixing the raw material with a good solution, into the reaction vessel, the polymerization reaction, the reaction temperatures are -20 -125 deg.] C polymerization time 30-300 minutes, typically carried out in the polymerization step, to prepare a copolymer polyol sulfonates.

本发明提供的磺酸盐共聚物适用于包括:化工、石油、纺织、电力、造纸等工业用水,如:循环冷却水、空调水、锅炉水、油田注水、饮用水、中水和废水等的分散阻垢、缓蚀、絮凝处理。 Sulfonate copolymers suitable for the present invention is provided comprising: a chemical, oil, textile, electricity, paper and other industrial water, such as: cooling water, air conditioning water, boiler water, oil field water, drinking water, waste water and the like dispersing scale and corrosion inhibition, flocculation. 本发明的优点:本发明提供的磺酸盐共聚物呈浅黄色或琥珀色粘稠液体,固含量≥30%,分子量为1000-10000,PH值=1-2,游离单体含量≤1.0-240。 Advantages of the invention: The present invention provides a copolymer of sulfonate as a pale yellow or amber viscous liquid, solid content of ≥30%, a molecular weight of 1000-10000, PH value = 1-2, the free monomer content ≤1.0- 240. 它做分散阻垢剂、缓蚀剂、絮凝剂,用于处理化工、石油、纺织、电力、造纸等工业用水,以及高PH值的高碱高硬度的循环冷却水、中水和废水,且除垢效率达85%以上。 It does dispersing scale inhibitors, corrosion inhibitors, flocculants, circulating cooling water for processing a high hardness high alkali chemical, oil, textile, electricity, paper and other industrial water, and the PH value is high, the water and waste water, and cleaning efficiency of 85% or more.

本发明的制备方法简单,以水做溶剂原料价格便宜,不需浓缩步骤,反应一次完成,减少中间步骤提高生产重复性,保证质量,缩短生产周期,减少人工成本大大降低,该方法产品粗收率达95%以上。 The preparation method is simple, with water as solvent inexpensive raw material, without the concentration step, once the reaction is completed, an intermediate step to reduce the repetitive increase production, quality assurance, shorten the production cycle, reducing labor costs greatly reduced, which yield a crude product more than 95%.

下面结合附图及实施例对本发明进行详细说明:图1是本发明的工艺流程图实施例1:首先取单体A:AMPS;单体B:C4H2O3(顺丁烯二酸酐),引发剂:过氧化氢,A∶B∶引发剂20∶75∶5(重量比)称料,以水为溶剂,通过物料管线抽人各自配料釜中,配料所需的水由水高位槽提供。 The present invention is described in detail in conjunction with the accompanying drawings and the following embodiments: FIG. 1 is a process flow diagram of an embodiment of the present invention: First, take the monomers A: AMPS; monomer B: C4H2O3 (maleic anhydride), initiator: hydrogen peroxide, A:B: 20:75:5 initiators (weight ratio) of said material, water as a solvent, a line drawn through the material of their respective ingredients kettle ingredients required by the water header tank of water. 配好的单体和引发剂通过管线抽至混合单体高位槽及引发剂高位槽中。 Monomer and initiator with a good monomer mixture pumped to a header tank through line header tank and the initiator. 进行聚合反应,其引发剂溶液及混合单体经过流量调节阀门和视镜,通过加料管加入反应釜中反应式为: Polymerization reaction, which monomer mixture and the initiator solution flow rate adjusting valve and through the mirror, the reaction kettle was added through the feed tube to the reaction formula: 反应时温度保持在80℃下,反应125分钟。 When the reaction temperature was maintained at 80 ℃, reaction was 125 minutes. 反应釜设有蒸汽及循环冷却水的出入口,蒸汽由反应釜侧面进入夹套,由反应釜侧下方经过疏水器等排入地沟;循环冷却水则由下至上,流向与蒸汽相反,经过夹套后进入回水管线。 Reactor with steam and circulating cooling water inlet and outlet, steam enters the reactor jacket side by side below the reaction vessel and the like through the trap into the trench; circulating cooling water by the first, opposite to the flow of the steam through the jacket after entering the return line. 反应过程中,反应釜内的反应蒸汽由冷凝器上部进入其管程,凝液由其下部经管线回至反应釜中。 During the reaction, the reaction in the reactor is steam which enters the tube from the top condenser, the lower portion of the condensate therefrom back to the reactor vessel via a line. 冷却水走壳程,下进上出,生成的二元磺酸盐共聚物从反应釜输出。 Cooling water on the shell side, the entry on the generated binary output from the reactor sulfonate copolymer. 本装置的物料输送均采用真空输送,因此设置了真空泵。 The present material handling apparatus are conveyed by vacuum, the vacuum pump is thus provided. 本实施例生成的二元磺酸盐共聚物用于处理废水,其分散阻垢效率达85%。 Sulfonate copolymer of the present embodiment generates two yuan embodiment for treating waste water, the dispersion scale up to 85% efficiency.

Claims (5)

  1. 1.一种磺酸盐共聚物,其组成包括单体A:AMPS;单体B:顺丁烯二酸酐和引发剂,其特征在于:单体A与单体B和引发剂聚合成二元磺酸盐共聚物的组成配比为A∶B∶引发剂=5-50∶10-90∶1-6(重量比),结构为: A sulfonate copolymer A monomer composition comprising: the AMPS; B monomers: maleic anhydride and an initiator, wherein: monomer A and monomer B and a polymerization initiator into two yuan sulfonate composition ratio of copolymer = 5-50:10-90:1-6 A:B: initiator (weight ratio), with the structure: 聚合成三元磺酸盐共聚物的组成配比为A∶B∶C∶引发剂=5-30∶10-80∶20-50∶1-6,结构为: Polymerized into three yuan sulfonate composition ratio of copolymer = 5-30:10-80:20-50:1-6 A:B:C: initiator, with the structure: 其中单体C:丙烯酸、丙烯腈或丙烯酸酯;其中n=10-100;m=10-100;p=10-100;分子量为1000-10000;其中所述的AMPS为2-丙烯酰胺基-2-甲基丙烷磺酸-1。 Wherein monomer C: acrylic acid, acrylonitrile or acrylate; wherein n = 10-100; m = 10-100; p = 10-100; molecular weight 1000-10000; wherein said AMPS is 2-acrylamido-- -1 2-methylpropane sulfonic acid.
  2. 2.如权利要求1所述的一种磺酸盐共聚物,其特征在于:所述的引发剂为:高锰酸钾、次氯酸钠、过氧化氢或过硫酸盐。 2. An sulfonate copolymer according to claim 1, wherein: said initiator: potassium permanganate, sodium hypochlorite, hydrogen peroxide or persulfate.
  3. 3.一种制备权利要求1所述的磺酸盐共聚物的方法,其特征在于:选取单体A:AMPS、单体B:顺丁烯二酸酐,以水为溶剂,在加入引发剂生成二元磺酸盐共聚物时,按A∶B∶引发剂5-50∶10-90∶1-6(重量比)配料;生成三元磺酸盐共聚物时,按A∶B∶C∶引发剂=5-30∶10-80∶20-50∶1-10(重量比)配料,其中单体C:丙烯酸、丙烯腈或丙烯酸酯,将上述原料溶液混合配好,送入反应釜内按常规聚合工艺进行聚合反应,其反应温度-20℃-125℃,反应时间30-300分钟。 The method of claim 1 for preparing a salt of the copolymer as claimed in claim 3, wherein: selecting monomer A: AMPS, monomer B: maleic anhydride, with water as the solvent, adding the initiator to generate when two yuan sulfonate copolymer, press A:B: 5-50:10-90:1-6 initiator (ratio by weight) ingredients; generating three yuan sulfonate copolymer, press A:B:C: = 5-30:10-80:20-50:1-10 initiators (weight ratio) of ingredients, wherein monomer C: acrylic acid, acrylonitrile, or acrylic ester, the raw material solution was mixed with a good, fed into the reactor by conventional polymerization process the polymerization reaction, the reaction temperature is -20 ℃ -125 ℃, the reaction time of 30-300 minutes.
  4. 4.如权利要求3所述的磺酸盐共聚物的制备方法,其特征在于:所述的引发剂为:高锰酸钾、次氯酸钠、过氧化氢或过硫酸盐。 4. The method as recited in claim 3 sulfonate copolymer, wherein: said initiator: potassium permanganate, sodium hypochlorite, hydrogen peroxide or persulfate.
  5. 5.一种权利要求1所述的磺酸盐共聚物的应用,其特征在于:磺酸盐共聚物作为处理水的分散阻垢剂、缓蚀剂、絮凝剂。 Application of a salt according to claim 5. A copolymer, wherein: sulfonate copolymer as a dispersing treatment water scale inhibitors, corrosion inhibitors, flocculants.
CN 97103642 1997-03-25 1997-03-25 Co-polymer of sulfonate, the prepn. method and use thereof CN1082058C (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US5238637A (en) * 1991-06-07 1993-08-24 Rhone-Poulenc Fibres Process for obtaining polyamide yarns with better output efficiency
US5300231A (en) * 1992-08-05 1994-04-05 Calgon Corporation Controlling silica/silicate deposition using phosphonate combinations
US5366637A (en) * 1993-05-24 1994-11-22 Betz Laboratories, Inc. Method for dewatering municipal solid waste refuse

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238637A (en) * 1991-06-07 1993-08-24 Rhone-Poulenc Fibres Process for obtaining polyamide yarns with better output efficiency
US5300231A (en) * 1992-08-05 1994-04-05 Calgon Corporation Controlling silica/silicate deposition using phosphonate combinations
US5366637A (en) * 1993-05-24 1994-11-22 Betz Laboratories, Inc. Method for dewatering municipal solid waste refuse

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