CN104229757B - 一种将污酸净化处理返回流程再利用的方法 - Google Patents
一种将污酸净化处理返回流程再利用的方法 Download PDFInfo
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- CN104229757B CN104229757B CN201410492776.XA CN201410492776A CN104229757B CN 104229757 B CN104229757 B CN 104229757B CN 201410492776 A CN201410492776 A CN 201410492776A CN 104229757 B CN104229757 B CN 104229757B
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- acid
- supernatant
- adsorption tower
- heavy metal
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- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000002253 acid Substances 0.000 title claims abstract description 65
- 238000000746 purification Methods 0.000 title claims abstract description 22
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- 239000006228 supernatant Substances 0.000 claims abstract description 54
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 49
- 150000002500 ions Chemical class 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 238000004062 sedimentation Methods 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound 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O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound 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OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000003860 storage Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 230000001698 pyrogenic Effects 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 4
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 7
- 238000007792 addition Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound 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[Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 4
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound 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[Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
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O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 208000008425 Protein Deficiency Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 230000024126 agglutination involved in conjugation with cellular fusion Effects 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound 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Abstract
本发明公开一种将污酸净化处理返回流程再利用的方法,将硫酸生产过程中的先采用圆锥沉降槽沉降分离污酸中的固体颗粒和重金属杂质,酸上清液放入上清液储槽中后用泵均匀加入到吸附塔中,并且加入重金属离子捕捉剂和絮凝剂,使上清液中的重金属离子与重金属离子捕捉剂和絮凝剂生成絮状沉淀物而加速沉降,污酸上清液中的微小重金属离子被填装在吸附塔上部硅藻土颗粒吸附后产出较为纯净的稀酸,稀酸经过滤、换热器降温后,返回硫酸生产流程使用;吸附塔底部定期排放出的底流,经压滤后产生的滤渣返火法系统使用,产出的滤液再次返回到吸附塔中进行处理。
Description
技术领域
[0001] 本发明涉及一种将污酸净化处理返回流程再利用的方法,特别是一种对烟气制酸 过程中产生污酸进行净化处理的方法,实现污酸总量减少的同时返回流程再利用的方法。
背景技术
[0002] 在冶金生产过程中,通常用含量为5~10%的高浓度二氧化硫的烟气用于制备硫酸。 制酸过程中,必须对烟气中所含的尘、酸雾等成分在净化阶段采用水洗或酸洗喷淋,实现除 尘、降温、除水和除酸雾及杂质的目的,以满足硫酸的正常生产。净化工序产生的污酸含有 铅、锌、汞、砷、铜、镉等重金属,其后续处理过程一直是是环保难题。目前普遍采用石灰中和 沉淀法处理污酸,会产生大量石膏渣,环保压力突出,石灰中和污水处理流程长,污水硬度 高,无法满足生产使用。
发明内容
[0003] 本发明目的在于克服上述现有技术不足,发明一种将污酸净化处理返回流程再利 用的方法,特别是将污酸净化回用工艺以及工艺流程中涉及的设备操作单元。
[0004] 本发明一种将污酸净化处理返回流程再利用的方法步骤如下:
[0005] 1)将硫酸生产过程中净化洗涤工序产生的污酸,采用圆锥沉降槽沉降分离,先将 污酸中的固体颗粒和重金属杂质进行初步分离;
[0006] 2)经圆锥沉降槽沉降处理后的污酸上清液放入上清液储槽中,待进行吸附处理。
[0007] 3)储槽中的污酸上清液用栗均匀加入到吸附塔中,污酸上清液加入过程中通过两 套独立的加药装置,分别将重金属离子捕捉剂和絮凝剂加入到污酸上清液输送管道中,添 加了重金属离子捕捉剂和絮凝剂的污酸上清液在管道中混合后加入吸附塔中进行处理。
[0008] 4)添加了重金属离子捕捉剂和絮凝剂的污酸上清液在吸附塔中发生反应,污酸上 清液中的重金属离子会与重金属离子捕捉剂和絮凝剂生成絮状沉淀物而加速沉降,污酸上 清液中的微小重金属离子被填装在吸附塔上部硅藻土颗粒吸附后产出较为纯净的稀酸,稀 酸从吸附塔的上部溢流口流出经过滤、换热器降温后,返回硫酸生产流程使用;
[0009] 5)吸附塔底部定期排放出的底流,经压滤后产生的滤渣返火法系统使用,产出的 滤液再次返回到吸附塔中进行处理。
[0010] 所述的步骤(1)污酸在圆锥沉降池中的沉降时间控制在3-10分钟,污酸中的固体 颗粒和重金属杂质在圆锥沉降槽中进行自由沉降分离。
[0011] 所述的步骤(2)过程所使用的重金属离子捕捉剂为二硫代胺基甲酸盐类衍生物, 按重量百分比计,重金属离子捕捉剂加入量为〇. 01~〇. 015%
[0012] 所述的步骤(2)过程所使用的絮凝剂为聚合氯化铝,按重量百分比计,絮凝剂加入 量为0.008~0.010%
[0013] 所述的步骤(3),污酸上清液通过在吸附塔中的吸附时间为2-5分钟。其目的是使 加入重金属离子捕捉剂和絮凝剂的污酸上清充分形成絮状物沉淀实现沉降分离。
[0014] 所述的吸附过程所使用的吸附塔中装填有硅藻土颗粒填充层,硅藻土颗粒直径为 1·5~2·0mm〇
[0015] 本发明采用污酸净化回用的方法,将污酸进行净化处理并回用,解决污酸处理成 本高、环境问题突出等问题。
附图说明
[0016] 图1为本发明工艺流程图。
[0017] 图2为本发明使用的吸附塔结构示意图。
[0018] 图3为本发明斜隔板部件的结构示意图。
[0019] 图4为本发明布水隔栅板部件的结构示意图。
[0020] 图5为本发明单个滤帽部件的结构示意图。
[0021] 图中:丨一支架、2-吸附塔、3-进液管、4一清液出口、5-排气口、6-沉渣出口、 7一滤帽花板、8-滤帽、9 一娃藻土颗粒、10-斜隔板、11 一布水隔栅板,12-连接杆,13滤水 栅。
[0022] L一两块斜隔板之间的间隔距尚;S-两块布水隔栅板之间的间隔距尚;β-斜隔板 的倾角;α-布水隔栅板倒V字形的内角。
具体实施方式
[0023] 本发明污酸净化吸附塔包括:支架,所述支架在吸附塔塔体下部对整个塔体起到 支撑作用;吸附塔塔体由玻璃钢制作的罐体。进液管,由吸附塔塔体中部引入,穿过布水隔 板,进液管的进液口位于吸附塔塔体下部;清液出口,位于吸附塔上部,用于将净化后的清 液排出;排气口,位于吸附塔塔体顶部与脱吸塔相连接用于将净化过程产生的废气排出;沉 渣出口,位于吸附塔塔体底部,其结构呈圆锥体,用于将净化过程产生的底流排出;滤帽花 板,位于吸附塔塔体内壁的上部,其作用将罐体隔断为上、下两个部分,为中间分布带螺纹 的孔用于安装滤帽8;滤帽,为中空结构,通过螺纹固定于滤帽花板的下部,滤帽下部由间隙 〈1.3mm的滤水栅13组成,其作用是对净化后的溶液起到过滤作用。上清液通过滤帽8向上渗 出,而硅藻土颗粒无法通过滤水栅13停留在滤帽花板下部。硅藻土颗粒,粒径范围为1.3_ 1.5 mm;比表面积:450-500m2/g;孔隙率:45-50%;平均孔径:12-16 nm,密度大约为水的1/ 10,吸附能力很强。硅藻土颗粒带有对偶极子,可吸附进入悬浮层的细小悬浮物,并且可以 结合为高效无机絮凝剂吸附污酸中的其他重金属;斜隔板,两块之间倾角呈45度角,两块斜 隔板之间以30-35cm的间隔均匀排布,斜隔板主要是促进净化液中的悬浮物加速沉降。污酸 上清液中70-80%的悬浮物得到沉降;布水隔栅板呈倒的V字形,其V字形内角α为60度角,角 为布水隔栅板的顶部,开口为布水隔栅板的下部,两块布水隔栅板的间隔距离S为30-36cm, 布水隔栅板呈上层与下两层交替均匀分布。目的是让金属吸附剂和絮凝剂与污酸上清液混 合、充分反应。
[0024] 本发明设备使用操作过程如下:
[0025] (1)经过圆锥沉降槽处理并加入重金属离子捕捉剂和絮凝剂的污酸上清液,通过 吸附塔进液管3加入到吸附塔中,随着污酸上清液不断加入吸附塔中的液面不断升高,通过 布水隔栅板11时污酸上清液与重金属离子捕捉剂和絮凝剂充分混合;吸附塔中污酸上清液 不断加入液面均匀上升,经过斜隔板10时污酸上清液中的悬浮物进行沉降,悬浮物落入吸 附塔底部,污酸上清液中的大部分杂质在此沉降脱出。吸附塔中污酸上清液不断加入液面 逐渐上升,残留在污酸上清液的悬浮物与硅藻土颗粒9发生反应,污酸上清液中的悬浮物被 硅藻土颗粒9吸附,在硅藻土颗粒9表面形成滤饼层,随着滤饼层变厚,重力大于浮力,则掉 落进入底部浓缩液区。此外硅藻土颗粒9还带有对偶极子,可以吸附进入悬浮层的细小悬浮 物,并结合为高效无机絮凝剂,吸附污酸上清液中的其他重金属。液面不断上升,经过吸附 处理的上清液通过滤帽8上的滤水栅后逐渐向滤帽花板7上渗透,当上清液达到上清液出口 位置时自然流出,经过滤、板式换热器降温后返回流程使用。
[0026] (2)由于硅藻土粒径大于滤帽8上滤水栅的宽度,被有效隔离在滤帽花板7下方,随 着硅藻土颗粒表面吸附的滤饼层逐渐变厚,重力大于浮力,则掉落进入底部浓缩液区,与浓 缩区的杂质一同沉入吸附塔底部通过吸附塔沉渣出口 6定期排出。
[0027] (3)吸附过程产生的气体经吸附塔排气口5排出,送入脱吸塔进行处理。
[0028]本发明方法工艺流程如下:
[0029] 1)将硫酸生产过程中净化洗涤工序产生的污酸,采用圆锥沉降槽沉降分离,先将 污酸中的固体颗粒和重金属杂质进行初步分离;
[0030] 2)经圆锥沉降槽沉降处理后的污酸上清液放入上清液储槽中,待进行吸附处理。
[0031] 3)储槽中的污酸上清液用栗均匀加入到吸附塔中,污酸上清液加入过程中通过两 套独立的加药装置,分别将重金属离子捕捉剂和絮凝剂加入到污酸上清液输送管道中,添 加了重金属离子捕捉剂和絮凝剂的污酸上清液在管道中混合后加入吸附塔中进行处理。
[0032] 4)添加了重金属离子捕捉剂和絮凝剂的污酸上清液在吸附塔中发生反应,污酸上 清液中的重金属离子会与重金属离子捕捉剂和絮凝剂生成絮状沉淀物而加速沉降,污酸上 清液中的微小重金属离子被填装在吸附塔上部硅藻土颗粒吸附后产出较为纯净的稀酸,稀 酸从吸附塔的上部溢流口流出经过滤、换热器降温后,返回硫酸生产流程使用;
[0033] 5)吸附塔底部定期排放出的底流,经压滤后产生的滤渣返火法系统使用,产出的 滤液再次返回到吸附塔中进行处理。
[0034] 步骤(1)污酸在圆锥沉降池中的沉降时间控制在3-10分钟,污酸中的固体颗粒和 重金属杂质在圆锥沉降槽中进行自由沉降分离。
[0035] 步骤(3)过程所使用的重金属离子捕捉剂为二硫代胺基甲酸盐类衍生物,按重量 百分比计,重金属离子捕捉剂加入量为〇. 01~〇. 015%。
[0036] 作用机理具是:重金属捕捉剂含有大量的极性基 n $ &基团,在常温和很宽 C-Ξ 的PH值条件范围内,与污酸中的?132+、2112+、〇12+、0(1 2+、取2+上2+等多种重金属离子进行化学 反应,并在短时间内迅速生成不溶性、低含水量、容易过滤去除的絮状沉淀,从而达到从水 中去除重金属离子的目的。
[0037] 步骤(3)过程所使用的絮凝剂为聚合氯化铝,按重量百分比计,絮凝剂加入量为 0.008~0.010%。作用机理具有凝聚和絮凝两种作用的过程。
[0038] 步骤(4),污酸上清液通过在吸附塔的时间为2-5分钟。其目的是使加入重金属离 子捕捉剂和絮凝剂的污酸上清充分形成絮状物沉淀实现沉降分离。
[0039]吸附过程所使用的吸附塔中装填有硅藻土颗粒填充层,硅藻土颗粒直径为1.5~ 2.0mm〇
[0040] 实施例1:将一级动力波排除的污酸加入圆锥沉降槽,沉降时间控制在3-10分钟 内,使污酸中的固体颗粒和重金属杂质在圆锥沉降槽中发生自由沉降分离。圆锥沉降槽上 端溢流口产生的清液进入上清液储槽,在沉降槽分离的含固体颗粒和重金属杂质的底流进 行过滤分离另行处理。
[0041] 经过圆锥沉降槽溢流出来含有的重金属离子的上清液放入到储槽中等待吸附处 理。需要对污酸上清液进行处理时,用栗将污酸上清液均匀加入的吸附塔中,分别按0.01~ 0.015%的重金属离子捕捉剂和0.008~0.010%的絮凝剂,通过两套加药装置分别加入到吸附 塔中进行处理。
[0042]吸附塔中填装有150~200mm的硅藻土颗粒,加入重金属离子捕捉剂和絮凝剂的污 酸上清通过吸附塔中硅藻土颗粒填充层,加速污酸上清中的重金属离子会与重金属离子捕 捉剂和絮凝剂生成絮状物沉淀而沉降分离,同时污酸中的微小重金属离子被硅藻土颗粒吸 附实现净化的目的。
[0043] 净化后稀酸从吸附塔上部溢流至回用液储槽,经过板式换热器降温之后返回硫酸 生产流程使用,实现污酸回用。
[0044] 吸附塔底部定期排放出的底流,经压滤后产生的滤渣返火法系统使用,产出的滤 液再次返回到吸附塔中进行处理。
[0045] 污酸加入吸附塔的过程中,添加了重金属捕捉和絮凝助剂两种化学药剂,两种药 剂的作用过程及原理如下:
[0046]重金属离子捕捉剂:为二硫代胺基甲酸盐类衍生物,作用机理具是:重金属捕捉剂 含有大量的极性基ίΤ 1基团,在常温和很宽的PH值条件范围内,与废水中的Cu2+、Cd2 +、Hg2+、Pb2+、Mn2+、Ni 2+、Zn2+、Cr3+等多种重金属离子进行化学反应,并在短时间内迅速生成 不溶性、低含水量、容易过滤去除的絮状沉淀,从而达到从水中去除重金属离子的目的。
[0047] 絮凝助剂:为聚合氯化铝作用机理是凝聚和絮凝两种作用的过程。凝聚过程是胶 体颗粒脱稳并形成细小的凝聚体的过程;絮凝过程是所形成的细小的凝聚体在絮凝助剂的 桥连下生成大体积的絮凝物的过程。
[0048] 凝聚作用是颗粒由小到大的量变过程,而絮凝作用是量变过程达到一定程度时的 质变过程,絮凝作用是由若干个凝集作用组成的、是凝聚作用的结果。而凝聚作用是絮凝作 用的原因。
[0049] 通过重金属捕捉剂和絮凝助剂加速絮状物的产生,同时通过硅藻土材料进行吸 附,从而实现了污酸的净化处理。净化后稀酸从吸附塔顶部溢流至回用液储槽,经过滤、板 式换热器降温之后返回到二级动力波补水处,实现污酸回用。
[0050] 本发明采用污酸净化回用的方法,将污酸进行净化处理并回用,解决污酸处理成 本高、环境问题突出等问题。
[0051 ]污酸净化处理回用的方法实施前后效果对比:
[0052]污酸上清液成分
[0053] 表1 污酸化学成分分析结果
[0054]
[0055]处理后的污酸成分 Γηη口主〇 、V^而余、/么 ;丑山门谷出乂乂乂乂士口来〇/-、
Claims (6)
1. 一种将污酸净化处理返回流程再利用的方法,其特征在于步骤如下: 1) 将硫酸生产过程中净化洗涤工序产生的污酸,采用圆锥沉降槽沉降分离,先将污酸 中的固体颗粒和重金属杂质进行初步分离; 2) 经圆锥沉降槽沉降处理后的污酸上清液放入上清液储槽中,待进行吸附处理; 3) 储槽中的污酸上清液用栗均匀加入到吸附塔中,污酸上清液加入过程中通过两套独 立的加药装置,分别将重金属离子捕捉剂和絮凝剂加入到污酸上清液输送管道中,添加了 重金属离子捕捉剂和絮凝剂的污酸上清液在管道中混合后加入吸附塔中进行处理; 4) 添加了重金属离子捕捉剂和絮凝剂的污酸上清液在吸附塔中发生反应,污酸上清液 中的重金属离子会与重金属离子捕捉剂和絮凝剂生成絮状沉淀物而加速沉降,污酸上清液 中的微小重金属离子被填装在吸附塔上部硅藻土颗粒吸附后产出较为纯净的稀酸,稀酸从 吸附塔的上部溢流口流出经过滤、换热器降温后,返回硫酸生产流程使用; 5) 吸附塔底部定期排放出的底流,经压滤后产生的滤渣返火法系统使用,产出的滤液 再次返回到吸附塔中进行处理。
2. 根据权利要求1所述的一种将污酸净化处理返回流程再利用的方法,其特征在于步 骤(1)污酸在圆锥沉降槽中的沉降时间控制在3-10分钟,污酸中的固体颗粒和重金属杂质 在圆锥沉降槽中进行自由沉降分离。
3. 根据权利要求1所述的一种将污酸净化处理返回流程再利用的方法,其特征在于步 骤(3)过程所使用的重金属离子捕捉剂为二硫代胺基甲酸盐类衍生物,按重量百分比计,重 金属离子捕捉剂加入量为〇. 01~〇. 015%。
4. 根据权利要求1所述的一种将污酸净化处理返回流程再利用的方法,其特征在于步 骤(3)过程所使用的絮凝剂为聚合氯化铝,按重量百分比计,絮凝剂加入量为0.008~ 0.010%〇
5. 根据权利要求1所述的一种将污酸净化处理返回流程再利用的方法,其特征在于步 骤(4),污酸上清液在吸附塔中的吸附时间为2-5分钟,其目的是使加入重金属离子捕捉剂 和絮凝剂的污酸上清液充分形成絮状物沉淀实现沉降分离。
6. 根据权利要求1所述的一种将污酸净化处理返回流程再利用的方法,其特征在于吸 附过程所使用的吸附塔中装填有硅藻土颗粒填充层,硅藻土颗粒直径为1.5~2.0mm。
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