CN105517689A - 一种使用腐殖试剂和灰黄霉试剂过滤并回收温室气体的方法 - Google Patents
一种使用腐殖试剂和灰黄霉试剂过滤并回收温室气体的方法 Download PDFInfo
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- CN105517689A CN105517689A CN201480042518.XA CN201480042518A CN105517689A CN 105517689 A CN105517689 A CN 105517689A CN 201480042518 A CN201480042518 A CN 201480042518A CN 105517689 A CN105517689 A CN 105517689A
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- reagent
- humic
- alkalization
- gas
- liquid filtering
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Links
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Abstract
本发明提供了一种用于除去来自气体的多种污染物的高度碱化的腐殖和灰黄霉过滤试剂。从气体流中除去的污染物可以包括但不限于,二氧化碳、硫氧化物、氮氧化物、氢硫化物、放射性核素、硫醇、氨、有毒金属,颗粒、挥发性蒸汽和有机物。本发明还包括过通过使用用作土壤肥度的高度碱化的腐殖和灰黄霉过滤剂处理过滤试剂,释放过滤试剂中的二氧化碳,将液体的过滤试剂转换成固体以处理或用来作为水、废物和化学品的污染物除去过滤剂。
Description
背景技术
本发明涉及过滤气体,并且,更具体地,涉及一种使用腐殖(humic)过滤试剂和灰黄霉(fulvic)过滤试剂过滤并回收来自气体源的有害污染物的方法。
目前,不同种类的气体可能会引起污染和令人不愉快的气味。气体流包括多种通常排放到大气中的污染物。烟气是一种通过烟道排出到大气中的气体,所述烟道是输送来自壁炉、烤炉(oven)、熔炉(furnace)、锅炉或蒸汽发生器的废气的管道或通道。烟气通常是发电厂产生的燃烧废气。烟气组分取决于所燃烧的物质,但是它通常包括氮气、二氧化碳和水蒸气以及过量的氧气。该气体流还包括污染物,例如颗粒物(煤烟灰)、一氧化碳、氮氧化物、硫氧化物。这些气体中的很多可能都对环境有害。
家禽养殖是饲养家养的鸟类如鸡、火鸡、鸭和鹅,目的是为了收获用作食品的肉或蛋。在密集的肉鸡棚中,空气可能会由于来自鸡粪中的氨而变得高度污染,这可能会伤害鸡的眼睛和呼吸系统,并且能够引起它们腿(称为跗关节烧伤)和脚的痛苦的烧伤。进一步地,氨可能会引起恶臭的气味,这对农民和周围居民来说可能是不愉快的。
可以看出,用来收集多种不同气体源中释放的有害污染物的试剂是非常必要的。
发明内容
本发明一方面中,一种过滤气体的方法包括:将气体通过含有腐殖和灰黄霉质的高度碱化的液体过滤试剂。
本发明的另一方面中,一种过滤方法包括:将气体流通过含有腐殖和灰黄霉质的高度碱化的液体过滤试剂,以形成废的高度碱化的液体过滤试剂,交联废的高度碱化的液体过滤试剂以形成固体过滤剂。
本发明的又一方面中,除去有气味的化学品和微生物的方法包括:通过在室内喷洒高度碱化的腐殖和灰黄霉液体过滤试剂来处理充满气体的室(chamber),其中,所述气体含有包括氨的有气味的化学品,其中,所述气体还含有多种微生物和孢子,其中,所述处理降低了氨的水平,并且至少部分杀死了多种微生物和孢子。
通过参考随后的附图、说明书和权利要求可以更好地理解本发明的这些和其他特征、方面和优点。
附图说明
图1是煤燃烧气体和合成气的过滤流程示意图;
图2示出了通过本发明的腐殖和灰黄霉过滤试剂吸收来自煤燃烧气体和合成气的CO2。
具体实施方式
下面的详细描述是实施本发明的示范实施例的当前预期的最佳方式。以下描述不用来限制本发明,而仅仅是用来阐述本发明的一般原则,因为本发明的范围最好由所附的权利要求来限定。
本发明包括利用天然的有机试剂来除去多种污染物,从气体流中除去的污染物可以包括但不限于二氧化碳、硫氧化物、氮氧化物、氢硫化物、硫醇、氨、有毒金属、颗粒、挥发性蒸汽和有机物。本发明进一步包括通过使用用作土壤肥度的天然有机过滤剂的方式处理过滤剂,释放过滤剂中的二氧化碳,将液体过滤剂转换成固体以处理或用来作为水、废物和化学品的污染物除去过滤剂。
本发明的天然有机试剂是含有腐殖和灰黄霉质的高度碱化的过滤剂,腐殖和灰黄霉质可以以液态形式存在,然后转变成固体形式。腐殖和灰黄霉过滤剂的液体形式是一种独特创新的捕获CO2的途径。一旦CO2被捕获,液体试剂可能就会转变成固体过滤剂以除去废水中的多种污染物。腐殖和灰黄霉过滤试剂是一种煤衍生的有机腐殖液体产品,在小试规模的测试中被证实是可行的,能够除去煤燃烧气体中的100%的温室气体(GHG)。另外,腐殖和灰黄霉液体过滤试剂能够除去NOx,氮氧化物的前驱体,这有比CO2以及SOx和来自矿物燃料例如煤炭和石油燃烧的有毒微量金属高大约200倍的GHG潜能。来自燃烧气体的这些多种污染物的除去可以通过将气体通过液体腐殖和灰黄霉过滤试剂而实现。当气体通过容器时,可以与气体流共流喷洒或者与气体流逆流喷洒所述试剂。本发明也可以设置成独立的塔式反应中的低成本处理方式,以及提供一种实用划算的方式来改进现有的通常用于烟气处理的SOx净化器中的液体试剂。
所述液体过滤试剂可以是煤衍生的有机腐殖产品。所述液体腐殖和灰黄霉试剂具有多种官能团,包括羧基、羟基、烯醇和其碳基体(carbonmatrix)。所述试剂具有多种吸附、螯合和离子交换性能,因此能够和来自各种介质的多种有机和无机化学品结合。用过的液体过滤试剂接下来可以交联以形成固体过滤剂用于处理水或化学品。由于具有多种结合位点,所述固体过滤剂已经成功地发展成为用于除去多种污染物的水过滤剂。
腐殖和灰黄霉过滤试剂可衍生自腐殖酸(Humicacid),腐殖酸是一种黑色至棕色、高度官能化、富含碳的高分子。这种化学品的结构组成和性能已经成为世界上众多高校和研究所广泛研究的课题。腐殖酸多功能的特征性能可以包括:高阳离子交换能力、螯合金属的能力、吸附有机物的能力和高保水能力。已发现腐殖酸分子有卓越的表现,不仅表现在均一化学成分方面,而且就在捕获金属离子能力方面也有相似的属性。它是一种稳定的分子,其是我们地球上排在沉积岩、矿物燃料和海洋后的第四大碳库。另外,在土壤中的有机腐殖质是末端的(terminal),并且由于独特的分子组成而不会被进一步矿化。腐殖质在高度碱化的溶液中变的是可溶的,在pH<2时通过质子化而沉淀。与其相关联的次要组分被称为灰黄霉酸,且灰黄霉酸在所有的pH条件下都保持水溶性。
腐殖酸资源包括煤炭例如褐煤,泥炭,堆肥,湖泊、河流等的底泥。液体腐殖和灰黄霉过滤试剂的生产包括从富含腐殖质的煤炭中提取腐殖酸。腐殖酸的提取可以使用或不使用微生物而进行。利用微生物产生腐殖酸的例子可以包括如下方法,该方法可以包括使用有氧微生物消化煤炭,接下来在碱性条件下提取水溶性腐殖酸。煤炭可以使用源自白蚁内脏的微生物的联合体处理,本文称为消化的Mic-1处理。煤炭可以在有氧条件下温和地与水混合形成浆液。本方法中使用的菌浓度可以是煤炭、水和菌的混合物重量的约1%-20%。混合物中的煤炭浓度可以是混合物重量的约0.01%-50%。该方法可以产生接近95%的煤炭中腐殖酸的转化。
提取的水溶性腐殖酸可以制成有特定腐殖酸含量的高度碱化的腐殖和灰黄霉过滤试剂。例如,腐殖酸可以和碱溶液混合,例如但不限于,氢氧化钾、氢氧化钠、氨水等。腐殖酸和碱溶液的混合物形成了高度碱化的腐殖和灰黄霉液体过滤试剂。在某些实施方式中,高度碱化的腐殖和灰黄霉液体过滤试剂可以具有规定浓度,约0.5N至约10N,约1N至约9N,约2N至约8N,约3N至约7N,约4N至约6N,或者约5N。腐殖和灰黄霉液体过滤试剂的高度碱化方面允许过滤剂捕获来自气体流的大量的CO2。
在某些实施方式中,可以通过使用催化剂增加对CO2和其它温室气体的捕获。用来提高CO2捕获的催化剂可以包括多功能固体例如但是不限于,沸石、矾土等。进一步地,可以使用过渡金属例如但是不限于,钴、铜、镍、锌、钒等。进一步地,可以使用带有配体的过渡金属复合物例如但不限于,1,4,7,10-四氮杂环十二烷配合物(cyclen)和1,4,8,11-四-吖环四癸烷配合物(cyclam)。
如上所述,腐殖和灰黄霉液体过滤试剂用于除去来自气体流的多种污染物。腐殖酸可以在高碱度下制备,这有助于使得气体通过过滤试剂而从燃烧气体中结合所关注的污染物。之前和之后的傅里叶变换红外光谱(FTIR)分析证实CO2和腐殖分子结合并形成了碳酸盐、碳酸氢盐和CO2-腐殖酸复合有机化合物。小试规模可行性测试结果显示腐殖和灰黄霉过滤剂除去0.7千克每加仑,相反的是在相同条件下使用碱溶液除去了0.2千克每加仑。因此,本发明相比于对照组多捕获了超过3倍的CO2。由于本发明的高碱度,NOx和SOx也可被捕获,有毒金属例如汞、砷等被吸附在腐殖分子上。
一旦液体腐殖和灰黄霉过滤试剂被用来捕获气体流中的污染物,废的腐殖和灰黄霉液体过滤试剂可以变成固体腐殖和灰黄霉过滤剂。在这种实施方式中,废的腐殖和灰黄霉液体过滤试剂可以聚合或交联。通过交联腐殖和灰黄霉液体过滤试剂,形成了水不溶的聚合物,随着pH值的升高,降低了吸附剂的溶解度。腐殖酸的活性基团可以由钙保护。交联的腐殖和灰黄霉液体过滤试剂交联后即使有钠离子存在下在接近中性pH时也具有较低的溶解度。
任何常规的交联剂都可以用来交联腐殖和灰黄霉液体过滤试剂以产生不溶的腐殖和灰黄霉固体过滤剂。用于产生的交联剂可以为醛类和氧化还原酶。这些产品表现出较高pH下显著降低的溶解度。例如,当使用戊二醛或者戊二醛与无机酸(HCl、HNO3、H2SO4、H3PO4等)的混合物时,所得的交联腐殖酸具有在钠离子存在下的接近中性pH时的水中较低的溶解度。
可以用来交联腐殖酸的醛类化合物是具有1至22个碳原子的脂肪醛或芳香醛。所述醛类化合物可以被任何不会对醛类的交联能力产生不利影响的取代基取代,所述醛类化合物可以是饱和的或者不饱和的。所述醛类化合物可以是芳香醛,例如为苯甲醛、甲基苯甲醛(o-、m-或p-)或水杨醛。可以使用用来交联腐殖和灰黄霉液体过滤试剂的任何类型的氧化还原酶,包括过氧化物酶和氢化酶。
使用转化的腐殖和灰黄霉固体过滤剂除去来自废水的环境污染物依赖于腐殖酸的多官能团,包括羧基、羟基、烯醇和其碳基体,这赋予了它多种吸附、螯合和离子交换性能。因此,腐殖和灰黄霉固体过滤剂能够结合来自多种废水流的多种有机和无机化学品。金属例如氮、氧或硫可以通过杂原子与腐殖质的碳骨架相结合。金属的结合是通过羧基和酚氧基而发生的。进一步地,氮和硫对金属结合具有积极作用。腐殖和灰黄霉固体过滤剂具有2-5毫克当量每克的较高阳离子交换能力。但是,腐殖和灰黄霉固体过滤剂的使用寿命取决于废水中的污染物浓度。
上述的腐殖和灰黄霉过滤试剂可以用来除去其它气体源的污染物。例如,腐殖和灰黄霉过滤试剂可以除去有气味的化学品,例如来自于禽舍等的氨。氨可能由微生物的活动和化学品而释放。本发明能够捕获空气中的有气味的化学品,也能消除产生有气味化学品的微生物和化学品。可以通过使用腐殖和灰黄霉液体过滤试剂喷洒被化学品、生物质和放射性核素污染的表面来处理禽舍等,这会大幅降低有气味物质和污染物。进一步地,可以将试剂喷洒到被有气味化学品污染的空气中,从而能够除去空气中的有气味物质和污染物。
应当被理解的是,前面的与本发明示范实施例和不偏离本发明精神和范围的修改设置于接下来的权利要求中。
实施例1
测试使用的是合成气以及煤燃烧气。小试规模的示意图如图1所示。将腐殖和灰黄霉液体过滤试剂加入至填满有玻璃珠的柱状反应器中。柱状反应器被腐殖和灰黄霉液体过滤试剂填满并保持环境条件。合成气在气体气瓶中进行预混合,合成气的组成(重量%):H24.5%,CO10%,N225%,CO230.5%,CH430%,并从柱状反应器底部通过。在处理前后将气体样品从隔板中取出通过气相色谱进行CO2、SOx、NOx的分析。通过水置换法进行已处理气体体积的测定。
对于煤炭的测试,伴随着空气流从空气气瓶中通入管式炉中,将煤炭样品在加热到800℃的管式炉中燃烧。将燃烧气通入烧瓶中以除去任何煤烟灰,然后在腐殖和灰黄霉液体过滤试剂的柱状反应器中进行处理。气体组成和气体体积的测定方法与合成气的相似,除了有毒金属的分析。使得处理过的气体发泡成氧化性酸用来捕获气体流中的金属,然后使用电感耦合等离子体进行金属分析。对低阶煤和高阶煤都进行了测试。煤炭样品也进行了有毒金属掺杂:砷、镉、铬、汞和铅以增加浓度,从而使它们在燃烧气中以相对高于煤炭中所得固有浓度的浓度存在。这使得后续的实验设定中使用少量的煤炭燃烧进行分析变得可行。小试规模的原理的结果如图2所示。
实施例2
对于有气味物质的测试,通过向密闭室内的家禽垫料上喷洒腐殖和灰黄霉液体试剂进行氨控制和缓解它们形成的测试。氨水平首先从平均50ppm升至100ppm,随着氨产生的化学品在24小时以升计的水解,氨水平降低至平均25ppm水平,以满足规定的限制的需要。同时也分析了消除的已处理的梭状芽胞杆菌孢子和沙门氏菌,梭状芽胞杆菌芽孢和沙门氏菌不仅会形成有气味的化学品,还会增加疾病。
Claims (20)
1.一种过滤气体的方法,该方法包括:将气体通过含有腐殖和灰黄霉质的高度碱化的液体过滤试剂。
2.根据权利要求1所述的方法,其中,所述高度碱化的液体过滤试剂由腐殖酸和灰黄霉酸与碱溶液结合所形成。
3.根据权利要求2所述的方法,其中,所述碱溶液包括氢氧化钾、氢氧化钠、氨水、或者它们的组合。
4.根据权利要求1所述的方法,其中,所述气体为气体流。
5.根据权利要求5所述的方法,其中,高度碱化的过滤试剂除去来自气体流的多种污染物。
6.根据权利要求6所述的方法,其中,所述多种污染物包括二氧化碳、硫氧化物、氮氧化物、氢硫化物、硫醇、氨、放射性核素、有毒金属、颗粒、挥发性蒸汽和有机物。
7.根据权利要求1所述的方法,其中,所述方法还包括将气体通过高度碱化的过滤试剂以形成废的高度碱化的过滤试剂的步骤。
8.根据权利要求6所述的方法,其中,所述方法还包括交联废的高度碱化的过滤试剂以形成固体过滤剂的步骤。
9.根据权利要求7所述的方法,其中,所述方法还包括使用固体过滤剂过滤水基物质的步骤。
10.根据权利要求1所述的方法,其中,所述高度碱化的液体过滤试剂具有超过或等于0.5N的规定浓度。
11.根据权利要求1所述的方法,其中,所述高度碱化的液体过滤试剂含有包括多功能固体、过渡金属、过渡金属复合物或其组合的催化剂。
12.一种过滤方法,该方法包括:
将气体流通过含有腐殖和灰黄霉质的高度碱化的液体过滤试剂,以形成废的高度碱化的液体过滤试剂;以及
交联废的高度碱化的液体过滤试剂以形成固体过滤剂。
13.根据权利要求12所述的方法,其中,所述高度碱化的液体过滤试剂由腐殖酸和灰黄霉酸与碱溶液结合所形成。
14.根据权利要求13所述的方法,其中,所述碱溶液包括氢氧化钾、氢氧化钠、氨水、或者它们的组合。
15.根据权利要求12所述的方法,其中,高度碱化的过滤试剂除去来自气体流的多种污染物。
16.根据权利要求15所述的方法,其中,所述多种污染物包括二氧化碳、硫氧化物、氮氧化物、氢硫化物、硫醇、氨、有毒金属、颗粒、挥发性蒸汽和有机物。
17.根据权利要求12所述的方法,其中,所述方法还包括使用固体过滤剂过滤水基物质的步骤。
18.根据权利要求12所述的方法,其中,所述高度碱化的液体过滤试剂具有超过或等于0.5N的规定浓度。
19.一种除去有气味的化学品和微生物的方法,该方法包括:
通过在室内喷洒高度碱化的腐殖和灰黄霉液体过滤试剂来处理充满气体的室;
其中,所述气体含有包括氨的有气味的化学品,其中,所述气体还含有多种微生物和孢子;
其中,所述处理降低了氨的水平,并且至少部分杀死了多种微生物和孢子。
20.根据权利要求19所述的方法,其中,所述室内为禽舍,且所述微生物包括梭状芽胞杆菌和沙门氏菌。
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US11286433B2 (en) | 2017-08-01 | 2022-03-29 | Gaps Technology, Llc | Compositions and methods for remediating hydrogen sulfide in hydrocarbon based liquids |
US11420883B2 (en) * | 2017-08-30 | 2022-08-23 | Chemtreat, Inc | Method and system for controlling odor in water system |
EA202090158A1 (ru) * | 2018-04-23 | 2021-02-26 | Гэпс Текнолоджи, Ллк | Композиции и способы для удаления сероводорода и других загрязнений из жидкостей на основе углеводородов и водных растворов |
US10913911B1 (en) * | 2019-09-20 | 2021-02-09 | Gaps Technology Llc | Chemical compositions and treatment systems and treatment methods using same for remediating H2S and other contaminants in gasses |
US11549064B2 (en) | 2019-09-20 | 2023-01-10 | Gaps Technology, Llc | Chemical compositions and treatment systems and treatment methods using same for remediating H2S and other contaminants in fluids, including liquids,gasses and mixtures thereof |
US11919827B2 (en) | 2020-04-30 | 2024-03-05 | Nuorganics LLC | System and method for producing an organic fertilizer from waste gases or liquids |
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