TWI532688B - Sludge dewatering with dual polymer conditioning - Google Patents
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本案係主張2011年10月25日申請之中國申請案序號201110344579x優先權之PCT申請案,其揭示在此以全文引用的方式併入本文中。 This is a PCT application filed on Oct. 25, 2011, which is hereby incorporated by reference in its entirety in its entirety in its entirety herein in
本揭示係關於用於協助污泥脫水的組成物和方法。 The present disclosure relates to compositions and methods for assisting sludge dewatering.
大量污泥產生於處理污水和工業廢水之活性污泥過程中。目前,污泥處理成本佔一個典型污水處理廠(“WWTP”)營運成本的25-45%。預計該成本隨掩埋場和焚燒成本增加而不斷上升,尤其是在土地空間有限的國家和地區。即使在脫水過程後,典型的污泥含有顯著量的水(按重量計為70-85%)。如此高水含量大幅增加污泥處置成本,因此對污水處理廠盡可能提高其脫水效率是非常可取的。 A large amount of sludge is produced in the process of treating activated sludge from sewage and industrial wastewater. Currently, sludge treatment costs account for 25-45% of the operating costs of a typical wastewater treatment plant (“WWTP”). This cost is expected to increase as landfills and incineration costs increase, especially in countries and regions where land space is limited. Typical sludge contains significant amounts of water (70-85% by weight) even after the dewatering process. Such high water content greatly increases the sludge disposal cost, so it is highly desirable to have the sewage treatment plant increase its dewatering efficiency as much as possible.
在脫水過程中,污泥通常使用基於聚丙烯醯胺之陽離子聚合物(絮凝劑)作調理。然後藉由一個物理方法,諸如離心、帶式壓力或濾壓來將經調理的污泥脫水。絮凝劑能導致膠體和其他懸浮粒聚集,從而提高污泥的沉降率和過濾性。 In the dehydration process, the sludge is usually conditioned with a polyacrylamide-based cationic polymer (flocculant). The conditioned sludge is then dewatered by a physical method such as centrifugation, belt pressure or filtration. The flocculant can cause the colloid and other suspended particles to aggregate, thereby increasing the sedimentation rate and filtration of the sludge.
因此,改進污泥脫水有存在需求。理想的是,改進過的污泥脫水將導致更便宜的污泥的處置費用。 Therefore, there is a need to improve sludge dewatering. Ideally, improved sludge dewatering will result in a lower cost of sludge disposal.
絮凝是污泥脫水關鍵步驟。本揭示提供一種藉由併入雙重聚合物調理方案來改進絮凝之方法。除了聚合物絮凝劑,聚合物凝聚劑也施加至污泥以提高絮凝效率。相較於傳統只有絮凝劑的調理,這種雙重聚合物調理方法能允許從污泥中除去更多的水,從而降低諸如污水處理廠之污泥處置成本。 Flocculation is a key step in sludge dewatering. The present disclosure provides a method of improving flocculation by incorporating a dual polymer conditioning scheme. In addition to the polymeric flocculant, a polymeric coagulant is also applied to the sludge to increase flocculation efficiency. This dual polymer conditioning process allows for the removal of more water from the sludge compared to conventional flocculating conditioning, thereby reducing sludge disposal costs such as sewage treatment plants.
因此,本揭示係朝向處理污泥的方法。該污泥含有水。此方法包括:提供該污泥;將聚合物凝聚劑與污泥混合以形成凝聚的污泥;將陽離子絮凝劑與該凝聚的污泥混合以形成絮凝凝聚的污泥;且從該絮凝凝聚的污泥中除去至少部分的水。該聚合物凝聚劑包括環氧氯丙烷和二甲胺之共聚物(“Epi-DMA”),二烯丙基二甲基氯化銨之均聚物(“polyDADMAC”),或兩者之組合。 Accordingly, the present disclosure is directed to a method of treating sludge. The sludge contains water. The method comprises: providing the sludge; mixing the polymer flocculant with the sludge to form agglomerated sludge; mixing the cationic flocculant with the coagulated sludge to form a flocculated coagulated sludge; and coagulating from the flocculation At least a portion of the water is removed from the sludge. The polymeric coagulant comprises a copolymer of epichlorohydrin and dimethylamine ("Epi-DMA"), a homopolymer of diallyldimethylammonium chloride ("polyDADMAC"), or a combination of the two .
本揭示的這些和其它特徵和優點,將從下面的詳細描述結合所附加的申請專利範圍而顯而易見。 These and other features and advantages of the present invention will be apparent from the appended claims.
本揭示的好處和優點對於相關領域中的一般技術人士於審查以下詳細描述和附圖後將變得更加顯而易見。 The advantages and advantages of the present disclosure will become more apparent to those of ordinary skill in the <RTIgt;
發明之詳細說明/較佳具體實例 Detailed Description of the Invention / Preferred Embodiment
雖然本揭示可以各種形式之具體實例表現,但下文係以目前之較佳具體實例來說明本揭示,並瞭解本文之揭示係被認為是本揭示之例示,且非意圖將本揭示限制於所描 述之特定具體實例中。 The present disclosure may be embodied in a variety of specific examples, but the present disclosure is described by way of a preferred embodiment of the present invention, and the disclosure of the present disclosure is considered to be illustrative of the present disclosure, and is not intended to limit the disclosure In the specific example described.
應當進一步暸解本說明書本章節段的標題,即“發明之詳細說明(Detailed Description of the Invention)”係涉及美國專利局的要求,並且不意味著,也不應該被推斷限制本文所揭示之標的。 The title of this section of the specification should be further understood, that is, the "Detailed Description of the Invention" is a requirement of the U.S. Patent Office and is not meant to be construed as limiting the subject matter disclosed herein.
本揭示係針對包含Epi-DMA或polyDADMAC,或兩者之組合的物質組成物的方法,該Epi-DMA可以是直鏈或交聯的。如果為交聯的,該交聯的Epi-DMA可以採用選自由胺,一級胺,2至6個碳原子之伸烷二胺,聚丙烯多胺,聚乙烯多胺,以及其組合所成之群組之交聯劑。在某些具體實例中,交聯劑係六亞甲基二胺。在某些具體實例中,Epi-DMA和/或polyDADMAC可具有從10萬道爾頓至300萬道爾頓之分子量。在某些具體實例中,分子量之範圍可以為從50萬道爾頓至200萬道爾頓。 The present disclosure is directed to a method of material composition comprising Epi-DMA or polyDADMAC, or a combination of both, which Epi-DMA can be linear or cross-linked. If crosslinked, the crosslinked Epi-DMA can be selected from the group consisting of amines, primary amines, alkylene diamines of 2 to 6 carbon atoms, polypropylene polyamines, polyethylene polyamines, and combinations thereof. Group of crosslinkers. In certain embodiments, the crosslinking agent is hexamethylenediamine. In certain embodiments, Epi-DMA and/or polyDADMAC can have a molecular weight from 100,000 Daltons to 3 million Daltons. In some embodiments, the molecular weight can range from 500,000 Daltons to 2 million Daltons.
污泥係一種複雜的凝膠樣物質,其可包括礦物顆粒,微生物,和其他物質。熟悉此項技術者將認知到,本揭示係關於任何種類的污泥。污泥的一個例子係來自廢水處理廠(“WWTPs”)的廢物。兩個廢水處理廠的例子係城市的和工業的。污泥顆粒的表面通常帶負電荷。在習知的污泥調理中,污泥係藉由基於聚丙烯醯胺的陽離子絮凝劑絮凝,該陽離子絮凝劑之分子量在5-15百萬克/莫耳的範圍內。 Sludge is a complex gel-like substance that can include mineral particles, microorganisms, and other materials. Those skilled in the art will recognize that the present disclosure pertains to any type of sludge. An example of sludge is waste from wastewater treatment plants ("WWTPs"). Examples of two wastewater treatment plants are urban and industrial. The surface of the sludge particles is usually negatively charged. In conventional sludge conditioning, the sludge is flocculated by a cationic guanamine-based cationic flocculant having a molecular weight in the range of from 5 to 15 gram per mole.
在此創新中,污泥首先以Epi-DMA、polyDADMAC或該兩者之組合的聚合物凝聚劑處理。如果選擇交聯Epi-DMA,該交聯劑可選自由胺,一級胺,2至6個碳原子 之伸烷二胺,聚丙烯多胺,聚乙烯多胺,或其組合所成之群組。在某些具體實例中,交聯劑係六亞甲二胺。已知六亞甲二胺也稱為己烷-1,6-二胺,1,6-二胺基己烷和1,6-己二胺。在某些具體實例中,該聚合物凝聚劑之分子量範圍係從50萬至300萬道爾頓。該污泥可為生物污泥,初級污泥,或生物污泥與初級污泥之混合物。 In this innovation, the sludge is first treated with a polymer coagulant of Epi-DMA, polyDADMAC, or a combination of the two. If cross-linked Epi-DMA is selected, the crosslinker can be selected from free amines, primary amines, 2 to 6 carbon atoms. A group of alkylene diamines, polypropylene polyamines, polyethylene polyamines, or combinations thereof. In certain embodiments, the crosslinking agent is hexamethylenediamine. Hexamethylenediamine is also known as hexane-1,6-diamine, 1,6-diaminohexane and 1,6-hexanediamine. In certain embodiments, the polymeric coagulant has a molecular weight ranging from 500,000 to 3 million Daltons. The sludge may be a biological sludge, a primary sludge, or a mixture of biological sludge and primary sludge.
初級絮凝物係在以凝聚劑處理時形成。例如,城市污泥樣品的平均粒徑在加入100ppm凝聚劑後從37微米增加至185微米。該初級絮凝物是肉眼可見的,且它們能於脫水之前藉由陽離子絮凝劑進一步絮凝。 Primary floes are formed when treated with a coagulant. For example, the average particle size of a municipal sludge sample increased from 37 microns to 185 microns after the addition of 100 ppm coagulant. The primary floes are visible to the naked eye and they can be further flocculated by a cationic flocculant prior to dehydration.
凝聚劑和絮凝劑的最佳劑量隨不同污泥而變化,且可經由瓶杯試驗(jar test)決定。由於減少的初級絮凝物之表面積和電荷需求,如果使用同樣的絮凝劑,在雙重聚合物方案的絮凝劑之最佳劑量能比僅有絮凝劑之方案減少30%-80%。 The optimum dosage of coagulant and flocculant varies with different sludges and can be determined by a jar test. Due to the reduced surface area and charge requirements of the primary floes, if the same flocculant is used, the optimum dosage of the flocculant in the dual polymer scheme can be reduced by 30%-80% compared to the flocculant alone.
本發明人已經發現,聚合物凝聚劑,特別是交聯的Epi-DMA對處理污泥特別有效。雖然不希望受到該理論的約束,誠信因為聚合物凝聚劑具有非常高的陽離子電荷密度,其與污泥顆粒的表面牢固地結合。該分子量較小的凝聚劑被認為允許該凝聚劑分子穿透污泥凝膠基質較深的內部。雖然傳統的無機凝聚劑諸如聚合氯化鋁顯示了類似的效果,本揭示的聚合物凝聚劑似乎導致該污泥顆粒聚集成初級絮凝物。從這些初級絮凝物建構成的完全形成之絮凝物具有更緊密的結構和更高的絮凝物強度,其結果是,在 脫水時能達成較高的污泥餅乾燥度。 The inventors have found that polymeric coagulants, especially cross-linked Epi-DMA, are particularly effective for treating sludge. While not wishing to be bound by this theory, it is believed that because polymer coagulants have a very high cationic charge density, they bind firmly to the surface of the sludge particles. The smaller molecular weight coagulant is believed to allow the coagulant molecules to penetrate the deeper interior of the sludge gel matrix. While conventional inorganic coagulants such as polyaluminium chloride have shown similar effects, the polymer coagulants disclosed herein appear to cause the sludge particles to aggregate into primary floes. The fully formed flocs formed from these primary floes have a tighter structure and higher floc strength, as a result of A high sludge cake dryness can be achieved when dewatering.
在某些具體實例中,Epi-DMA是由交聯劑交聯的。該交聯劑可以選自由胺,一級胺,2至6個碳原子之伸烷二胺,聚丙烯多胺,聚乙烯多胺,及其組合之所成之群組。在某些具體實例中,該交聯劑係六亞甲基二胺。 In some embodiments, Epi-DMA is crosslinked by a crosslinking agent. The crosslinking agent may be selected from the group consisting of amines, primary amines, alkylene diamines of 2 to 6 carbon atoms, polypropylene polyamines, polyethylene polyamines, and combinations thereof. In certain embodiments, the crosslinking agent is hexamethylenediamine.
在某些具體實例中,首先將聚合物凝聚劑加入該污泥。在某些具體實例中,可以加入以重量計大於10 ppm,但低於800 ppm濃度之聚合物凝聚劑。在某些具體實例中,該污泥中聚合物凝聚劑的總濃度以重量計大於10 ppm,但低於800 ppm。 In some embodiments, a polymeric coagulant is first added to the sludge. In certain embodiments, a polymeric coagulant having a concentration greater than 10 ppm by weight but less than 800 ppm can be added. In some embodiments, the total concentration of polymer coagulant in the sludge is greater than 10 ppm by weight, but less than 800 ppm.
在某些具體實例中,從該絮凝的污泥除去水係藉由物理方法進行。物理方法的例子包括,但不限於,過濾和離心。熟習污泥處理領域的技術者將容易地認知到方法是否為該術語含義內的物理方法。 In some embodiments, the removal of water from the flocculated sludge is performed by physical means. Examples of physical methods include, but are not limited to, filtration and centrifugation. Those skilled in the art of sludge treatment will readily recognize whether the method is a physical method within the meaning of the term.
在某些具體實例中,該絮凝劑是一種陽離子聚合物。特別合適的絮凝劑是基於聚丙烯醯胺。該絮凝劑可以是由一種或多種陽離子單體組成之陽離子聚合物。陽離子單體的例子包括單烯丙基胺,二烯丙基胺,乙烯胺,二烷基胺基烷基丙烯酸酯和甲基丙烯酸酯和它們的季鹽或酸式鹽,其中包括,但不限於,丙烯酸二甲胺基乙酯甲基氯化季鹽(“DMAEA-MCQ”),丙烯酸二甲胺基乙酯甲基硫酸季鹽,丙烯酸二甲胺基乙酯氯甲苯季鹽,丙烯酸二甲胺基乙酯硫酸鹽,丙烯酸二甲胺基乙酯鹽酸鹽,甲基丙烯酸二甲胺基乙酯甲基氯化季鹽,甲基丙烯酸二甲胺基乙酯甲基硫酸鹽 季鹽,甲基丙烯酸二甲胺基乙酯氯甲苯季鹽,甲基丙烯酸二甲胺基乙酯硫酸鹽,甲基丙烯酸二甲胺基乙酯鹽酸鹽,二烷基胺基烷基丙烯醯胺或甲基丙烯醯胺,和它們的季鹽或酸式鹽,如丙烯醯胺丙基三甲基氯化銨,二甲基胺基丙基丙烯醯胺甲基硫酸鹽季鹽,二甲基胺基丙基丙烯醯胺硫酸鹽,二甲基胺基丙基丙烯醯胺鹽酸鹽,甲基丙烯醯胺丙基三甲基氯化銨,二甲基胺基丙基甲基丙烯醯胺甲基硫酸酯季鹽,二甲基胺基丙基甲基丙烯醯胺硫酸鹽,二甲基胺基丙基甲基丙烯醯胺鹽酸鹽,丙烯酸二甲胺基乙酯,甲基丙烯酸二甲胺基乙酯,二烯丙基二乙基氯化銨和二烯丙基二甲基氯化銨(“DADMAC”)。烷基通常是C1至C4烷基。 In some embodiments, the flocculating agent is a cationic polymer. A particularly suitable flocculating agent is based on polypropylene decylamine. The flocculating agent can be a cationic polymer composed of one or more cationic monomers. Examples of cationic monomers include monoallylamine, diallylamine, vinylamine, dialkylaminoalkyl acrylates and methacrylates and their quaternary or acid salts, including but not Limited to dimethylaminoethyl acrylate methyl chloride quaternary salt ("DMAEA-MCQ"), dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate chlorotoluene quaternary salt, acrylic acid Methylaminoethyl sulfate, dimethylaminoethyl acrylate hydrochloride, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt , dimethylaminoethyl methacrylate chlorotoluene quaternary salt, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, dialkylaminoalkyl acrylamide Or methacrylamide, and their quaternary or acid salts, such as acrylamidopropyltrimethylammonium chloride, dimethylaminopropylpropenylamine methyl sulfate quaternary salt, dimethyl Aminopropyl acrylamide sulfate, dimethylaminopropyl propylene decylamine hydrochloride, methacrylamide propylamine trimethyl chloride Ammonium, dimethylaminopropyl methacrylamidamine methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide amine sulfate, dimethylaminopropyl methacrylamide hydrochloride Salt, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diallyldiethylammonium chloride and diallyldimethylammonium chloride ("DADMAC"). The alkyl group is usually a C 1 to C 4 alkyl group.
在某些具體實例中,該聚合物凝聚劑和該污泥於混合陽離子絮凝劑之前預混合。 In some embodiments, the polymeric coagulant and the sludge are premixed prior to mixing the cationic flocculant.
在某些具體實例中,該凝聚劑和/或絮凝劑於混合進行下加入。然而,可存在有其他技術免除該凝聚劑和/或絮凝劑於混合進行下加入的需要。這樣的技術可以是分散用噴嘴,諸如從60563美國伊利諾州Naperville 1601,West Diehl Road,Nalco公司之Nalco PARETO技術,或其他類似的技術。 In some embodiments, the coagulant and/or flocculant is added in admixture. However, there may be other techniques that eliminate the need for the coagulant and/or flocculant to be added under mixing. Such a technique may be a dispensing nozzle such as Nalco PARETO technology from 60563 Vail, Naperville 1601, West Diehl Road, Nalco, Illinois , or other similar technology.
給出下面的實施例,以便更好理解本揭示。這些實施例不應被解釋為將揭示的範圍限縮到超過所核准的申請專利範圍語言之揭示範圍。 The following examples are given to better understand the present disclosure. The examples are not to be construed as limiting the scope of the disclosure beyond the scope of the language of the claimed invention.
從城市污水處理廠取得污泥樣品(2.1%總懸浮固體(”TSS“))。該廠內的脫水污泥餅具有16.5%污泥餅固體含量。該陽離子絮凝劑係選自Nalco Core Shell ®絮凝劑系列。藉由混凝試驗器(jar tester)混合該污泥樣品和聚合物溶液,並紀錄經調理污泥的毛細吸引時間(“CST”)。具有最低CST值之聚合物濃度被決定為最佳聚合物劑量。然後將該經調理的汙泥在模擬工業帶壓設備的實驗室過濾裝置進行脫水。將所得的污泥餅在105℃下乾燥直到恆重且分析固體含量。從圖1中可以看出,僅有絮凝劑之調理方法具有約16%的污泥餅固體,而使用133 ppm的聚合物凝聚劑(具有的分子量為約150萬道爾頓之六亞甲基二胺交聯之Epi-DMA)該含量增加至約19%,且當使用著266 ppm的凝聚劑則進一步增加到約20%。該最佳絮凝劑劑量用量從約120-200 ppm減少至30-90 ppm。在133 ppm凝聚劑濃度之總污泥體積減少量為約16%。 Sludge samples (2.1% total suspended solids ("TSS")) were obtained from municipal wastewater treatment plants. The dewatered sludge cake in the plant has a 16.5% sludge cake solids content. The cationic flocculant is selected from the Nalco Core Shell® flocculant series. The sludge sample and polymer solution were mixed by a jar tester and the capillary attraction time ("CST") of the conditioned sludge was recorded. The polymer concentration with the lowest CST value was determined as the optimum polymer dose. The conditioned sludge is then dewatered in a laboratory filtration unit that simulates industrial pressurized equipment. The resulting sludge cake was dried at 105 ° C until constant weight and the solid content was analyzed. As can be seen from Figure 1, only the flocculant conditioning method has about 16% sludge cake solids, while 133 ppm polymer coagulant (having a hexamethylene group with a molecular weight of about 1.5 million Daltons) The content of diamine crosslinked Epi-DMA) increased to about 19% and was further increased to about 20% when 266 ppm of coagulant was used. The optimum flocculant dosage is reduced from about 120-200 ppm to 30-90 ppm. The total sludge volume reduction at 133 ppm coagulant concentration was about 16%.
從煉油廠污水處理廠取得污泥樣品(3.7%TSS)。該廠內的脫水污泥餅具有15.6%污泥固體含量。實驗草案類似於實施例1。從圖2中可以看出。該凝聚劑加絮凝劑方案的污泥餅固體含量為約21%,比僅有絮凝劑之方案高4-6%。該凝聚劑加絮凝劑的使用得到污泥總體積減少量為約20%。 Sludge samples (3.7% TSS) were obtained from the refinery wastewater treatment plant. The dewatered sludge cake in the plant has a 15.6% sludge solids content. The draft experiment is similar to Example 1. As can be seen from Figure 2. The coagulant plus flocculant solution has a sludge cake solids content of about 21%, which is 4-6% higher than that of the flocculant alone. The use of the coagulant plus flocculant results in a total sludge reduction of about 20%.
本文提及的所有專利,在此以全文引用的方式併入本文中,不論是否在本揭示之內文中明確地這樣做。 All of the patents mentioned herein are hereby incorporated by reference in their entirety for all of their entireties in their entireties.
在本揭示中,詞語“一種(a或an)”被理解為包括單數和複數。相反地,任何引用到複數項目,在適當的情況下,包括單數。 In the present disclosure, the word "a" or "an" is understood to include both singular and plural. Conversely, any reference to a plural item, where appropriate, includes the singular.
本文揭示的所有範圍和參數被理解為包括假設與包含其中的任何和所有子範圍,以及在該端點之間的每一個數字。例如,在指定的範圍“1至10”應視為包括(且包含)最小值1和最大值10之間的任何和所有的子範圍;即,所有始於最小值1或大於1(例如,1至6.1),和結束於最大值10或小於10(例如,2.3至9.4,3至8,4至7),且最後包含於該範圍內的每個數字1,2,3,4,5,6,7,8,9和10。 All ranges and parameters disclosed herein are understood to include the assumption and the inclusion of any and all sub-ranges thereof, and each number between the endpoints. For example, a specified range "1 to 10" should be considered to include (and include) any and all subranges between a minimum value of 1 and a maximum value of 10; that is, all starting from a minimum value of 1 or greater than 1 (eg, 1 to 6.1), and ending at a maximum of 10 or less than 10 (for example, 2.3 to 9.4, 3 to 8, 4 to 7), and finally including each number 1, 2, 3, 4, 5 within the range 6,6,8,9 and 10.
從前述觀察到,在不脫離本揭示新穎概念的真實精神及範圍的情況下,許多修飾和變化是可以完成的。應當理解到關於所說明的特定具體實例或實施例並不意欲也不應被推斷作為限制。本揭示欲藉由所附申請專利範圍涵蓋所有落入該申請專利範圍內的該等修飾。 From the foregoing, many modifications and changes can be made without departing from the true spirit and scope of the novel. It should be understood that the specific specific examples or embodiments described are not intended to be construed as limiting. The disclosure is intended to cover all such modifications as fall within the scope of the appended claims.
圖1是實施例1結果的圖形說明;及圖2是實施例2結果的圖形說明。 1 is a graphical illustration of the results of Example 1; and FIG. 2 is a graphical illustration of the results of Example 2.
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