CN104125856A - 废水和/或废气中的毒性有机物的分解方法 - Google Patents

废水和/或废气中的毒性有机物的分解方法 Download PDF

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CN104125856A
CN104125856A CN201380009951.9A CN201380009951A CN104125856A CN 104125856 A CN104125856 A CN 104125856A CN 201380009951 A CN201380009951 A CN 201380009951A CN 104125856 A CN104125856 A CN 104125856A
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弗朗茨·约瑟夫·菲利普
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COMMERZIALBANK MATTERSBURG IM
Commerzialbank Mattersburg im Burgenland AG
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Abstract

一种废水和/或废气中的毒性有机物的分解方法,其中含有毒性有机物的废水和/或废气(2)首先被送入到液态碱性的碱金属/碱土金属溶液/悬浮液水浴(3),成为去稳定的毒性有机物,然后含有去稳定的毒性有机物的溶液/悬浮液水浴(3)以上升的方式引入到设置于其之上的毛细管块(4),该毛细管块(4)由处理过的纸浆和混有膨润土,沸石和/或石灰的泥炭的混合物构成,该膨润土,沸石和/或石灰粒径小于200μm。

Description

废水和/或废气中的毒性有机物的分解方法
技术领域
[0001] 本发明涉及一种废水和/或废气中的毒性有机物的分解方法。如该毒性有机物包 括二噁英和呋喃。
背景技术
[0002] 用于纯化和控制废水和废气中臭味的生物过滤器在现有技术中已经为人所熟知。 该生物过滤器包括一个过滤层和导入饱和了蒸汽的原始气体的空气分配室。如树皮堆肥、 青草堆肥、地面根木、碎树皮、泥炭、椰子纤维等不同的堆肥以及这些材料的混合物可以被 用作供废水或废气穿过的过滤材料。此类生物过滤器与上游生物清洗器的结合使用在过滤 处理中也比较常见。
[0003] 废气、焚烧气体、工业废气等含有的剧毒有机物,二噁英和呋喃造成了更严重的问 题。在处理或纯化此类废气时,需要专门开发昂贵的高科技设备。
发明内容
[0004] 根据本发明,解决了该任务。载有毒性有机物的废水和/或废气首先被送入液态 碱性的碱金属/碱土金属溶液/悬浮液的水浴中,使毒性有机物去稳定,由此,该含有去稳 定的毒性有机物的溶液/悬浮液水浴以上升的方式传递给置于其上的毛细管块,该毛细管 块由处理过的木浆和混有膨润土、沸石和/或石灰的泥炭的混合物构成,膨润土、沸石和/ 或石灰的粒径小于200 μ m。
[0005] 然后,该毒性有机物以一种简单和有利的方式分裂或分解,并降解为对环境无害 的化合物,其可以被气态和/或液态的可能可重复使用的终产品带走,或直接释放到大气 中,该终产品按本方法形成。
[0006] 根据本发明,在该方法的一个优选的实施方式中,一层泥炭层被设置在毛细管块 之上。这种应急方法主要是出于安全因素而实施,以确保根据该方法的终产物中不再含有 毒性有机物。
[0007] 根据本发明所述的方法的另一特征,精磨浆作为毛细管块里的处理过的木浆使 用。这些精磨浆由机械方法生产的初级纤维物质构成,在这种情况下,木屑或磨木浆也可作 为替代品。
[0008] 木屑一般用作生产精磨木浆的起始材料,其中不同的方法均可用于加工,如热磨 法。热磨法是一个热机械处理操作,其先在预热器中用热蒸汽将木屑预热和软化,然后再在 研磨机中研磨成纤维。该精磨木浆通常用于生产MDF板(中等密度纤维板)。
[0009] 根据本发明所述的方法的一个特征,包括一个氢氧化钙碱化的硫酸钙的均质水溶 液/悬浮液,其用作溶液/悬浮液水浴。优选使用石灰碱化的石膏溶液/悬浮液,在这种情 况下,整个溶液/悬浮液中须呈现一种均匀分布的状态。然而,该溶液/悬浮液水浴中,也 可以是任何易得碱金属盐和/或其它碱土金属盐溶液/悬浮液,该碱金属盐和/或其它碱 土金属盐溶液/悬浮液经相应碱金属或其它碱土金属化合物碱化。
[0010] 根据本发明所述的方法的另一个特征,该碱金属或碱土金属溶液/悬浮液水浴的 pH值被设定在8到11之间,优选8到9之间。
[0011] 根据本发明,所有处理步骤的处理温度在1°C到25°C之间,优选3°C到4°C。根据 本发明所述的方法的另一个特征,所有处理步骤都在0. 2bar到0. 8bar的半真空下操作,优 选为 0. 5bar。
[0012] 通过结合了附图的如下具体实施例,详细介绍本发明的各个目标、特征、方面和有 益效果。在这些附图中,相似的部件由相似编号进行标记。
附图说明
[0013] 图1为本发明实施本发明方法中分解废水和/或废气中毒性有机物的示意性结构 图。参考说明书附图中的图说明根据本发明所述的方法,该图描述了在实施本发明方法中, 分解废水和/或废气中毒性有机物的示意性结构。
[0014] 图1中,处理罐1,废水和/或废气2,溶液/悬浮液水浴3,毛细管块4,纯泥炭层 5,终产物6。
具体实施方式
[0015] 处理罐1的下部区域填充有液态碱性的碱金属/碱土金属溶液/悬浮液水浴3,并 被引入含有毒性有机物的废水和/或废气2。该溶液/悬浮液水浴3由硫酸钙的均质水溶 液/悬浮液构成,优选混有氢氧化興(石灰)溶液/悬浮液碱化的石膏溶液/悬浮液。然 后该溶液/悬浮液水浴3的pH值被设定在8到11之间,优选地,pH值范围在8到9之间。 在此碱性介质中,被引入的废水和/或废气2含有的毒性有机物在溶液/悬浮液水浴3中 变得不稳定。
[0016] 毛细管块4由木浆,优选精磨浆,以及以一定的比例混合了膨润土,沸石和/或石 灰的泥炭构成,其中,膨润土、沸石和/或石灰的粒径小于200微米,毛细管块4相邻地设置 在溶液/悬浮液3上方,溶液/悬浮液3上方均构成了整个毛细管块。优选地,纸浆与均匀 分散的膨润土、沸石和/或石灰混合。均匀分散的塑料、混合塑料和塑料化合物也可以被添 加到毛细管块中。溶液/悬浮液主要通过毛细管力,持续地从溶液/悬浮液水浴3被毛细 管块4吸收,并通过毛细管块4传递。去稳定的毒性有机物在通过化学/物理处理的情况 下被分裂或降解,形成单个无害的化合物。该方法的所有处理步骤,都在1°C到25°C的处理 温度下进行,优选3°C到4°C。同时,该方法所有处理步骤都在0. 2bar到0. 8bar的半真空 下进行,优选〇. 5bar。
[0017] 作为一个安全因素,毛细管块4优选覆盖了纯泥炭层5(以虚线示出),以便可靠地 确保所有的毒性有机物确实分裂或分解为无害的化合物。
[0018] 然后被分解的对环境无害的化合物,可以被根据本方法形成的气态和/或液态的 可能可重复使用的终产物6走,或直接释放到大气中。
[0019] 关于根据本发明所述的方法的实施,可以发现,在整个过程中所使用的材料的各 组分,以及处于相应处理阶段的介质,通过连续测量受到监测控制,在这种情况下,根据不 同的要求,或作为测量结果的函数,进料和撤回是可控的。该应急方法至少可以用来支持该 过程的连续进行。
[0020] 然而,为了有效保证根据本发明所述的方法的持续运行,2个或更多的处理罐是并 排联接的。处理罐的单个部分操作类似过滤箱,其中它们在到达既定的测量限值时或之前, 或在相应的饱和过程中,作为持续发生的监控测量的函数被切换。即,在操作中的处理罐是 关闭的,并且至少一个并联罐在运转。在断开阶段中,各个处理部分所用的材料将被替换或 再生,所以至少有一个处理罐总是可用的,从而在一个连续实施过程的意义上,实现废水和 /或废气中的毒性有机物的分解方法。
[0021] 根据本发明所述的方法以下通过一个优选的实施方式进一步阐述。
[0022] 处理罐的下部腔室注入溶液/悬浮液水浴,该溶液/悬浮液水浴由氢氧化钙的均 质水溶液,其中悬浮着精细研磨的石灰和石膏。溶液/悬浮液水浴的pH值初始设置为9-10。 在有机材料的焚化过程中形成的废气,含有如氯代烃,二噁英和/或呋喃之类的毒性有机 物;该废气借助压缩机,在7bar到12bar的压强下,被引入该溶液/悬浮液水浴。填充有溶 液/悬浮液水浴的腔室借助压缩机,把压强保持在6bar到12bar之间。
[0023] 在废气的持续引入过程中,水浴的pH值降低,在这种情况下,结块石膏从氢氧化 钙溶液和石灰中形成。作为一个pH值持续测量的函数,形成的石膏被取出;而另一方面,氢 氧化钙溶液和石灰根据要求被添加。
[0024] 包含在废气中的毒性有机物在水浴室的碱性水性介质中去稳定,其中废气在溶液 /悬浮液水浴中拥有足够的停留时间是个重要的指标。
[0025] 在由一个设于处理罐的上部输出口的泵产生的0. 5bar到0. 8bar的半真空下,液 体介质被从水浴室吸入到设置在其上面的一个腔室,其中处理罐中建立的压强梯度能保证 废气在溶液/悬浮液水浴中拥有足够的停留时间。
[0026] 设于其上面的腔室填充有精磨浆构成的毛细管块。如果有的话,其它纤维材料如 大麻纸,麻,亚麻,棉,纤维素,塑料,混合塑料,在各种情况下它们被分离成纤维或被精细分 散。为了增加表面面积,如果有的话,生物炭与金属化合物混合,按照不超过总重量1 %的量 加入上述毛细管块中。
[0027] 在设于毛细管块下方的水浴室中变得不稳定的毒性有机物,分裂或分解成不再加 重环境负担的成分。
[0028] -个含泥炭层也被设置于毛细管块的腔室的上面,其中含有泥炭的比例不超过总 重量的5%,(如果可能,总重量的3% ),并具有相对于干质量的80%的含水量。根据本方 法这个含泥炭层并不是绝对必要的,但出于安全考虑,它的设置仅仅是为了使任何仍残留 于排出的液体介质的毒性化合物通过分解变为无毒。
[0029] 整个处理阶段的处理温度优选:TC到4°C。
[0030] 相对于处理系统输入口的废气流(称为原始气体)以及处理系统输出口的气流 (称为洁净气体)的各个组分的测量也与该过程一起进行。测定的数据见下面的列表1至 2 〇
[0031] 多氯代二苯并-对-二噁英和多氯二苯并呋喃的浓度如表所示。结果包括了 2, 3, 7, 8位取代的多氯代二苯并-对-二噁英(P⑶D)和多氯代二苯并呋喃(P⑶F)的总含 量,以及根据国际毒性当量因子(I-TEF)模型得到的关于2, 3, 7, 8-四氯二苯并对二噁英 T⑶D的毒性当量的计算。
[0032] 通过汇总所有17种同系物在国际毒性当量因子(I-TEF)模型中考虑的检出限浓 度和衡量与之相应的当量因子,毒性当量限制浓度可以被测定。此限制浓度规定了包含在 模型中的17种有毒的多氯代二苯并-对-二噁英(PCDD)和多氯代二苯并对呋喃(PCDF) 同系物在以检出限浓度精确地出现的情况下,理论上最大可能的毒性当量值。对于上述测 量问题,得到〇· 〇〇〇〇4ng/Nm3 (原始气体)和0· 0005ng/Nm3 (洁净气体)的PCDD和PCDF的 毒性当量限制浓度。
[0033] 表中指出,有毒的1,2, 3, 7, 8-五氯二苯并对二噁英(1,2, 3, 7, 8-P5CDF)不能通过 色谱与1,2, 3, 4, 8-五氯二苯并对二噁英(1,2, 3, 4, 8-P5⑶F)分离。这一点同样适用于化 合物 1,2, 3, 4, 7, 8-六氯二苯并对二噁英(1,2, 3, 4, 7, 8-H6CDF)和 1,2, 3, 4, 7, 9-六氯二苯 并对二噁英(1,2, 3, 4, 7, 9-H6⑶F)。这意味着,结果位于安全范围之内。
[0034] 表1 :多氯代二苯并-对-二噁英rcDD和多氯二苯并对呋喃roCF的测量结果
[0035] ^ 多氯代二苯并对二噁英和多氯二苯并对呋 喃 原始气体 洁净气体 I毒性当量 |毒性当 限制浓度 量限制 I-TEF 浓度 ____I-TEF
[ng/Nm,] [ngTE/Nm [ng/Nml [ngTE/N _I I Ί _ m-Ί
[0036] 2.3.7.8- 四氯二苯并对二噁英 I 0.0018^ 0.00179 0.0001^ 0.00005 _T4CDD_____ 1二3,7,8-五氯二苯并对二噁英~~0.0012 0.00060 0.0002 0.00011 _P5CDD_____ 1,2,3,4,7,8-六氯二苯并对二噁 0.0005 0.00005 0.0003 0.00003 芙 H6CDD 1,2,3,6,7,8-六氯二苯并对二噁 0.0008 0.00008 0.0007~~0.00007 _英 H6CDD_____ 1,2,3,7,8,9-六氯二苯并对二卩惡~~0.0020 0.00020 0.0006 0.00006 _英 H6CDD_____ 1,2,3,4,6,7,8--七氯二苯并对二0.0027 0.00003 0 0051 0.00005 _噁英 H7CDD_____ 八氯代二苯并对二噁英 0.0034 0.000003 0 0045 0.00000 _Q8CDD_____5 2.3.7.8- 多氣二苯并对二噁英 0 0124 0.0027 00115 0.0004 _PCDD_____ 2.3.7.8- 四氯代二苯并对呋喃 0.0236 0.00236 0.0010~~0.00010 _T4CDF_____ 1.2.3.7.8- 五氯代二苯并对呋喃 0.0073 0.00037 0.0010 0.00005 _P5CDF a)_____ 2.3.4.7.8- 五氯代二苯并对呋喃0.0209 0.0104 0.0018~~0.00091 _P5CDF_____ 1,2,3,4,7,8-六氯二苯并对呋喃 0.0039 0.00039 0.0020~~0.00020 _H6CDFh)_____ 1,2,3,6,7,8-六氯二苯并对呋喃 0.0037 0.00037 0.0020~~0.00020 _H6CDF_____ 1,2,3,7,8,9-六氯二苯并对呋喊~~0.0009 0.00009 0.0007~~0.00007 _H6CDF_____ 2.3.4.6.7.8- 六氯二苯并对呋喃 0.0054 0.00054 0.0020~~0.00020 _H6CDF_____ 1.2.3.4.6.7.8- 七氯代二苯并对 0.0067 0.00007 0.0109 0.00011 _吱喃 H7CDF_____ 1.2.3.4.7.8.9- -..b 氣代二苯并对 0.0011 0.00001 0 0017~~0.00002 _吱喃 H7CDF_____ 八氯代二苯并对呋喃 08CDF 0.0024 0.000002 0.0069 0.00000 7
[0037] 2,3,7,8-多氯二苯并对呋喃 0.076 0.0146 0.030 0.0019 _PCDF_____ 2,3,7,8-多氯二笨并对二噁英 0088 0.0174 0042 0.0023 PCDD +多氯二苯并对呋喃 _PCDF_____
[0038] 原始气体浓度可参照标准状态(0°C,1013hPa)以及干燥废气。
[0039] a)不能与1,2, 3, 4, 8-五氯代二苯并对呋喃P5CDF分离 [0040] b)不能与1,2, 3, 4, 7, 9-六氯代二苯并对呋喃H6CDF分离
[0041] 多环芳烃(PAH)的烟气浓度如表2所示。结果包含各数值,根据EPA得到的16个 多环芳烃PAH的总含量,以及根据DIN38409H13(6个化合物)得到的含量。多环芳烃PAH 的检出限在0. 0001 μ g/Nm3的范围内。
[0042] 表2 :多环芳烃PAH的测量结果
[0043] 参数 多环芳烃 原始气体 洁净气体 ___[μ8/ΝπΊλ] _^__139__0.79 _MM__27__0.052 _%__LI__0.011 f 4A 0.046 _#__27__0.40 _Μ__2^0__0.012 _ 58__0.084 _ft__5,3__0.071 _苯并(a)蒽__056__0.007 _Μ__095__0.011 苯并(B)焚蒽 0.69 0.0051
[0044] _苯并(k)焚蒽__018__0.0011 _苯并(a)范__026__0.0013 茚并(l,2,3-c,d ) tt__OJj__0.0031 苯并(g, h,i )北__037__0.0024 二苯并(ac,ah)蒽__0.042__0.0002 _PAH (EPA)ί〇__215__h5_ PAH (DIN 38409 HI3) h) 7,6 0.10
[0045] 原始气体浓度可参照标准状态(0°C,1013hPa)以及干燥废气。
[0046] a) 16个测量的多环芳烃的PAH (EPA)总和
[0047] b)下列6个多环芳烃的PAH(DIN38409H13)总和:
[0048] 荧蒽(C16H1Q),苯并(a)芘(C2QH12),苯并(b)荧蒽(C 2QH12)
[0049] 苯并(k)突蒽(C2QH12),苯并(g,h,i)花(C22H 12),
[0050] 茚并(1,2, 3-c,d)芘(C22H12)
[0051] 本检测结果表明,在该处理系统输出口的清洁气体的数值,要比该处理系统输入 口的原始气体的数值低很多。由于清洁气体管线到烟囱的连接区域的倒流烟气看来也可能 引起的洁净气体数值的失真。

Claims (8)

1. 一种废水和/或废气中的毒性有机物的分解方法,其特征在于,含有毒性有机物的 废水和/或废气首先送入到液态碱性的碱金属/碱土金属溶液/悬浮液水浴,成为去稳定 的毒性有机物,然后所述含有去稳定的毒性有机物的溶液/悬浮液水浴以上升的方式引入 到设置于其之上的毛细管块,所述毛细管块由处理过的纸浆和混有膨润土、沸石和/或石 灰的泥炭的混合物构成,所述膨润土,沸石和/或石灰粒径小于200 μ m。
2. 根据权利要求1所述的方法,其特征在于,所述毛细管块之上设置有一层泥炭层。
3. 根据权利要求1所述的方法,其特征在于,所述毛细管块内的处理浆为精磨浆。
4. 根据权利要求1所述的方法,其特征在于,相对于毛细管块,膨润土,沸石和/或石灰 的比例为 〇· 3to5wt %,优选 0· 5to lwt %。
5. 根据权利要求1所述的方法,其特征在于,所述溶液/悬浮液水浴为氢氧化钙碱化的 硫酸钙均质水溶液。
6. 根据权利要求1或5任一项所述的方法,其特征在于,所述碱金属/碱土金属溶液/ 悬浮液水浴的pH值的范围在8到11之间,优选8到9之间。
7. 根据权利要求1所述的方法,其特征在于,所有所述处理阶段的处理温度在1°C到 25°C之间,优选 3°C to4°C。
8. 根据权利要求1所述的方法,其特征在于,所述方法在所有所述处理阶段都在 0· 2bar toO. 8bar的半真空下操作,优选0· 5bar。
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