CN107915354A - 一种脱硫废水零排放及资源化利用装置和方法 - Google Patents
一种脱硫废水零排放及资源化利用装置和方法 Download PDFInfo
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- CN107915354A CN107915354A CN201810006394.XA CN201810006394A CN107915354A CN 107915354 A CN107915354 A CN 107915354A CN 201810006394 A CN201810006394 A CN 201810006394A CN 107915354 A CN107915354 A CN 107915354A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 122
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 77
- 230000003009 desulfurizing Effects 0.000 title claims abstract description 77
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound 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[Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000010802 sludge Substances 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound 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[Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound 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- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound data:image/svg+xml;base64,PD94bWwgdmVyc2lvbj0nMS4wJyBlbmNvZGluZz0naXNvLTg4NTktMSc/Pgo8c3ZnIHZlcnNpb249JzEuMScgYmFzZVByb2ZpbGU9J2Z1bGwnCiAgICAgICAgICAgICAgeG1sbnM9J2h0dHA6Ly93d3cudzMub3JnLzIwMDAvc3ZnJwogICAgICAgICAgICAgICAgICAgICAgeG1sbnM6cmRraXQ9J2h0dHA6Ly93d3cucmRraXQub3JnL3htbCcKICAgICAgICAgICAgICAgICAgICAgIHhtbG5zOnhsaW5rPSdodHRwOi8vd3d3LnczLm9yZy8xOTk5L3hsaW5rJwogICAgICAgICAgICAgICAgICB4bWw6c3BhY2U9J3ByZXNlcnZlJwp3aWR0aD0nMzAwcHgnIGhlaWdodD0nMzAwcHgnIHZpZXdCb3g9JzAgMCAzMDAgMzAwJz4KPCEtLSBFTkQgT0YgSEVBREVSIC0tPgo8cmVjdCBzdHlsZT0nb3BhY2l0eToxLjA7ZmlsbDojRkZGRkZGO3N0cm9rZTpub25lJyB3aWR0aD0nMzAwLjAnIGhlaWdodD0nMzAwLjAnIHg9JzAuMCcgeT0nMC4wJz4gPC9yZWN0Pgo8dGV4dCB4PSc2OS44JyB5PScxNzAuMCcgY2xhc3M9J2F0b20tMCcgc3R5bGU9J2ZvbnQtc2l6ZTo0MHB4O2ZvbnQtc3R5bGU6bm9ybWFsO2ZvbnQtd2VpZ2h0Om5vcm1hbDtmaWxsLW9wYWNpdHk6MTtzdHJva2U6bm9uZTtmb250LWZhbWlseTpzYW5zLXNlcmlmO3RleHQtYW5jaG9yOnN0YXJ0O2ZpbGw6IzNCNDE0MycgPk48L3RleHQ+Cjx0ZXh0IHg9Jzk3LjQnIHk9JzE3MC4wJyBjbGFzcz0nYXRvbS0wJyBzdHlsZT0nZm9udC1zaXplOjQwcHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojM0I0MTQzJyA+YTwvdGV4dD4KPHRleHQgeD0nMTE4LjYnIHk9JzE1NC4wJyBjbGFzcz0nYXRvbS0wJyBzdHlsZT0nZm9udC1zaXplOjI2cHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojM0I0MTQzJyA+KzwvdGV4dD4KPHRleHQgeD0nMTg2LjgnIHk9JzE3MC4wJyBjbGFzcz0nYXRvbS0xJyBzdHlsZT0nZm9udC1zaXplOjQwcHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojNUJCNzcyJyA+QzwvdGV4dD4KPHRleHQgeD0nMjE0LjQnIHk9JzE3MC4wJyBjbGFzcz0nYXRvbS0xJyBzdHlsZT0nZm9udC1zaXplOjQwcHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojNUJCNzcyJyA+bDwvdGV4dD4KPHRleHQgeD0nMjIyLjknIHk9JzE1NC4wJyBjbGFzcz0nYXRvbS0xJyBzdHlsZT0nZm9udC1zaXplOjI2cHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojNUJCNzcyJyA+LTwvdGV4dD4KPC9zdmc+Cg== data:image/svg+xml;base64,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 [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
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- 229910052801 chlorine Inorganic materials 0.000 description 4
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[Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
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- 239000002699 waste material Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound 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[OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound 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[Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound 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[N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating Effects 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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- 239000012535 impurity Substances 0.000 description 2
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- 238000006385 ozonation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound 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[NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances 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[Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound 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O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound 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Classifications
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F5/02—Softening water by precipitation of the hardness
Abstract
本发明公开了一种脱硫废水零排放及资源化利用装置和方法,应用于火电、化工、冶金等行业高盐废水处理技术领域,脱硫废水依次经过以下处理:预处理单元,降低脱硫废水中Ca2+、Mg2+和SO4 2‑的含量;深度处理单元,降低脱硫废水中SS、COD、硬度、NH3‑N和SO4 2‑的含量,深度处理单元与预处理单元相连;膜浓缩单元,得到浓盐水,膜浓缩单元与深度处理单元相连;中水回用单元,收集中水,并降低中水中的TDS含量,中水回用单元与膜浓缩单元相连;和双极膜水解离单元,得到氢氧化钠溶液和盐酸溶液,双极膜水解离单元与膜浓缩单元相连。本发明同时实现了脱硫废水的零排放和资源化利用,保护了环境,节约了能源,降低了废水处理的投入成本,设备运行稳定。
Description
一种脱硫废水零排放及资源化利用装置和方法
技术领域
[0001]本发明涉及火电、化工、冶金等行业高盐废水处理技术领域,具体而言,涉及一种 脱硫废水零排放及资源化利用装置和方法。
背景技术
[0002]近年来,国家在工业废水污染防治、提高废水利用率、污染排放总量控制等方面提 出了更加严格的要求,使得煤炭、电力、钢铁和化工等重点行业需要大力推广工业废水循环 利用技术,以达到零排放的目的。
[0003] 脱硫废水具有以下特点: (1)腐蚀性强,其中含有较多的酸性物质,这些酸性物质不仅会污染环境,而且对燃煤 电厂的机械设备产生腐蚀作用,导致设备受损。
[0004] (2)有较高的含盐量。
[0005] (3)硬度高,易结垢,脱硫废水中含有较多的钙离子和镁离子,同时硫酸钙处于过 饱和状态,在这种情况下,只要加热,脱硫废水就会结垢,同时,脱硫废水具有较强的硬度, 也会对脱硫设备产生严重的损害。
[0006] 现有技术中对工业废水的处理方式有: 石灰石-石膏法对火电、化工和冶金等行业中排放的烟气进行脱硫,但该方法产生了大 量的脱硫废水,废水成分复杂。
[0007] 其次,国内脱硫废水主要采用传统的中和-沉淀-絮凝方法,通过在废水中增加消 石灰、有机硫、絮凝剂和助凝剂等,去除废水中的重金属,最终经过PH调节处理后排放,该方 法排放的废水存在以下问题:(1)废水中TDS(水中溶解物质)含量高,且波动范围较大,其中 氯离子含量为15000-25000 mg/L,水中TDS含量越高,即代表水中杂质越多;(2)水质硬度 大,钙离子及镁离子含量较高,钙离子浓度达到1000-2000 mg/L,镁离子达到200-500 mg/ L; (3)COD含量较高,约为50-100 mg/L; (4)废水中含有少量的悬浮物、硅和氨氮等污染物。 [0008]为实现废水的零排放处理,防止水体TDS指标过高,含盐量过高,水质和土地盐碱 化,现有技术中常采用浓缩+蒸汽蒸发结晶法(专利文献:CN201410100547.9)或浓缩+烟道 余热蒸发结晶法(专利文献:CN201521064672.5),上述方法存在以下问题: (1) 采用蒸汽蒸发结晶时,由于高浓度氯化钠具有很强的氯离子腐蚀性,对蒸发结晶器 的材料要求很高,设备初始投入和运行成本较高; (2) 蒸发结晶过程中容易造成结晶器结垢,影响传热效率,运行稳定性较差; (3) 采用烟道余热蒸发结晶时,雾化喷嘴很容易堵塞,运行稳定性较差; (4) 蒸发结晶的产品品质较低,难以直接利用,产品盐的氯化钠含量较低,如果不采用 分盐方法,产品为混合盐,只能作为固废处理,如果采用分盐方法,结晶盐很难循环使用,只 能暂存在厂区内部。
发明内容
[0009] 本发明旨在一定程度上解决上述技术问题之一。
[0010] 有鉴于此,本发明提供了一种脱硫废水零排放及资源化利用装置和方法,同时实 现了脱硫废水的零排放和资源化利用,保护了环境,节约了能源,降低了废水处理的投入成 本,设备运行稳定。
[0011] 为了解决上述技术问题,本发明提供了 一种脱硫废水零排放及资源化利用装置, 包括: 预处理单元,用于降低脱硫废水中Ca2+、Mg2+和3〇42_的含量; 深度处理单元,用于降低脱硫废水中SS、C0D、硬度、NH3-N和S〇42_的含量,所述深度处理 单元与所述预处理单元相连; 膜浓缩单元,用于得到浓盐水,所述膜浓缩单元与所述深度处理单元相连; 中水回用单元,用于收集中水,并降低中水中的TDS含量,所述中水回用单元与所述膜 浓缩单元相连; 和双极膜水解离单元,用于得到氢氧化钠溶液和盐酸溶液,所述双极膜水解离单元与 所述膜浓缩单元相连, 所述深度处理单元包括依次连接的超滤装置、臭氧催化氧化装置、离子膜交换树脂装 置、膜脱氨装置和纳滤装置; 所述膜浓缩单元包括依次连接的反渗透装置和正渗透装置; 所述中水回用单元包括依次连接的中水回用原水箱和低压反渗透装置; 所述双极膜水解离单元包括依次连接的缓冲箱和双极膜水解离装置。
[0012] 进一步,所述反渗透装置包括依次连接的多段高压反渗透装置以及对应的产水 箱,每段高压反渗透装置的浓水作为下一段高压反渗透装置的进水,多段高压反渗透装置 的产水通过所述产水箱流至所述中水回用单元,最后一段高压反渗透装置的浓水流至所述 正渗透装置。
[0013] 进一步,所述预处理单元包括依次连接的废水调节池、一级反应箱、沉淀箱、二级 反应箱、微滤浓缩箱、微滤膜装置和微滤产水箱。
[0014] 进一步,所述废水调节池中设置有曝气搅拌装置。
[0015] 进一步,所述深度处理单元还包括超滤产水箱、纳滤缓冲箱和纳滤产水箱,所述超 滤产水箱与所述超滤装置相连,所述纳滤缓冲箱连接在所述膜脱氨装置和纳滤装置之间, 所述纳滤产水箱连接在所述纳滤装置的出水端。
[0016] 一种脱硫废水零排放及资源化利用方法,包括以下步骤: S1,预处理,脱硫废水进入预处理单元,对废水进行化学软化处理,除去废水中的沉淀, 分别将废水中的Ca2+、Mg2+、3〇42_浓度降低至20、15、1000 mg/L以下; S2,深度处理,经过S1处理后的脱硫废水进入深度处理单元,将脱硫废水中的SS、C0D、 硬度、NH3-N和S〇42_的浓度分别降低至2、20、10、1、100mg/L以下; S3,膜浓缩处理,经过S2处理后的渗透液经过膜浓缩单元,依次经反渗透和正渗透作 用,将软化水的TDS含量浓缩至200000mg/L以上,得到浓盐水; S4,中水回用处理,将S3处理后的产水收集后经中水回用单元,将产水中的TDS降低至 20mg/L,作为锅炉给水使用; S5,水解离处理,将S3处理后的浓盐水经双极膜水解离单元,得到资源化利用的氢氧化 钠溶液和盐酸溶液。
[0017] 进一步,所述预处理的步骤依次包括:将脱硫废水加入废水调节池中;向一级反应 箱的脱硫废水中加入氢氧化钙和氯化钙,降低脱硫废水中的Mg2+和S0,浓度;向沉淀箱中加 入絮凝剂;向二级反应箱中加入氢氧化钠和碳酸钠,降低脱硫废水中硬度;最后通过排污栗 排出所述沉淀箱中的污泥。
[0018] 进一步,所述深度处理的步骤包括:经过S1处理后的废水经超滤去除废水中悬浮 物;然后依次经过臭氧催化氧化、离子膜交换树脂、膜脱氨降低废水中C0D、硬度和NH3-N的 含量;然后进行纳滤作用将脱硫废水中的cr和s〇42-分开,得到主要含cr的渗透液和主要含 so,的浓缩液,所述浓缩液回到所述预处理单元,所述渗透液流至所述膜浓缩单元。
[0019] 进一步,所述膜浓缩处理过程包括:经过S2处理后的渗透液经过反渗透装置获得 产水和浓水,所述产水至所述中水回用单元,所述浓水至正渗透装置处理获得浓盐水。
[0020] 进一步,所述预处理单元的废水调节池中通入有压缩空气。
[0021] 本发明的技术效果在于:根据本发明的一种脱硫废水零排放及资源化利用装置和 方法,同时实现了脱硫废水的零排放和资源化利用,脱硫废水经过浓缩单元后直接进入离 子膜电解单元电解生成碱、氢气和氯气,其中碱和氯气为工业的原料,可以直接作为产品出 售,浓缩单元的产水经过中水回用单元处理后可以直接回收使用,真正实现了脱硫废水的 零排放。
[0022] 其次,本发明脱硫废水零排放投入成本和处理成本低,本发明不设置蒸发浓缩和 结晶单元,由于高氯离子腐蚀严重,对蒸发浓缩和结晶设备的材料要求很高,因此设备投资 很大。本发明避免了高昂设备的投资,使用反渗透膜浓缩和正渗透浓缩方法,而膜浓缩方法 运行成本很低,正渗透装置无高压设备,浓缩的运行成本很低,整个方法的浓缩单元,吨水 的处理成本低于二十元,因此处理成本很低。
[0023]另外,本发明实现了企业内的资源循环化利用。资源化的产品中水可以作为锅炉 的给水、氢氧化钠溶液和盐酸溶液可以直接在企业内循环使用,减少了药剂的使用量,降低 了成本。
附图说明
[0024]图1是根据本发明一种脱硫废水零排放及资源化利用装置的结构示意图。
[0025]图2是根据本发明一种脱硫废水零排放及资源化利用方法的步骤流程图。
[0026]其中,1 -预处理单元;2-深度处理单元;3_膜浓缩单元;4-中水回用单元;5-双极膜 水解离单元;11-废水调节池;12-—级反应箱;13-沉淀箱;14-二级反应箱;15-微滤浓缩箱; I6-微滤膜装置;17-微滤产水箱;21-超滤装置;22-超滤产水箱;23-臭氧催化氧化装置;24-离子膜交换树脂装置;25_膜脱氨装置;26-纳滤缓冲箱;27-纳滤装置;28-纳滤产水箱;31_ 弟一段局压反渗透装置;32_桌一段尚压反渗透浓水箱;33_第二段高压反渗透装置;34-第 二段高压反渗透浓水箱;35-正渗透装置;:36-正渗透汲取液再生装置;41-中水回用原水箱; 42-低压反渗透装置;51-缓冲箱;52-双极膜水解离装置。
具体实施方式
[0027]下面结合附图和具体实施例对本发明作进一步说明,以使本领域的技术人员可以 更好的理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
[0028]如图1所示,本发明提供了一种脱硫废水零排放及资源化利用装置,包括: 预处理单元1,用于降低脱硫废水中Ca2+、Mg2+和S0,的含量; 深度处理单元2,用于降低脱硫废水中SS(悬浮物)、⑶D(化学需氧量)、硬度、NH3-N(氨 氮)和S0,的含量,深度处理单元2与预处理单元1相连; 膜浓缩单元3,用于得到浓盐水,膜浓缩单元3与深度处理单元2相连; 中水回用单元4,用于收集中水(再生水),并降低中水中的(溶解性固体)含量,中水 回用单元4与膜浓缩单元3相连,中水即经过适当的处理,可达到一定的水质标准,满足某种 使用要求,可以进行有益使用的水,再生水成本较低,废水进一步处理转化为再生水,有利 于改善生态环境和实现水生态的良性循环; 和双极膜水解离单元5,用于得到氢氧化钠溶液和盐酸溶液,实现资源化利用,双极膜 水解离单元5与膜浓缩单元3相连, 深度处理单元2包括依次连接的超滤装置21、臭氧催化氧化装置23、离子膜交换树脂装 置24、膜脱氨装置25和纳滤装置27,深度处理单元2通过超滤装置21与预处理单元1相连,预 处理单元1处理后的水通过水栗泵入超滤装置21中; 膜浓缩单元3包括依次连接的反渗透装置和正渗透装置35; 中水回用单元4包括依次连接的中水回用原水箱41和低压反渗透装置42; 双极膜水解离单元5包括依次连接的缓冲箱51和双极膜水解离装置52,缓冲箱51用于 暂存水,双极膜水解离装置52用于获得氢氧化钠溶液和盐酸溶液。
[0029]根据本发明的一种脱硫废水零排放及资源化利用装置和方法,同时实现了脱硫废 水的零排放和资源化利用,脱硫废水经过浓缩单元后直接进入离子膜电解单元电解生成 碱、氢气和氯气,其中碱和氯气为工业的原料,可以直接作为产品出售,浓缩单元的产水经 过中水回用单元4处理后可以直接回收使用,真正实现了脱硫废水的零排放。
[0030] 其次,本发明脱硫废水零排放投入成本和处理成本低,本发明不设置蒸发浓缩和 结晶单元,由于高氯离子腐蚀严重,对蒸发浓缩和结晶设备的材料要求很高,因此设备投资 很大。本发明避免了高昂设备的投资,使用反渗透膜浓缩和正渗透浓缩方法,而膜浓缩方法 运行成本很低,正渗透装置无高压设备,浓缩的运行成本很低,整个方法的浓缩单元,吨水 的处理成本低于二十元,因此处理成本很低。
[0031] 另外,本发明实现了企业内的资源循环化利用。资源化的产品中水可以作为锅炉 的给水、氢氧化钠溶液和盐酸溶液可以直接在企业内循环使用,减少了药剂的使用量,降低 了成本。
[0032] 具体而言,反渗透装置包括依次连接的多段高压反渗透装置以及对应的产水箱, 每段高压反渗透装置的浓水作为下一段高压反渗透装置的进水,多段高压反渗透装置的产 水通过产水箱流至中水回用单元4,最后一段高压反渗透装置的浓水流至正渗透装置35。 [0033]根据本发明的一个具体实施例,经过深度处理后的渗透液首先经过第一段高压反 渗透装置31,由第一段高压反渗透装置31处理后生成产水和浓水,产水进入其对应的产水 箱;浓水通过第一段高压反渗透浓水箱32进入第二段高压反渗透装置33,由第二段高压反 渗透装置33处理后生成的产水进入其对应的产水箱,浓水进入第二段高压反渗透浓水箱 34,按照上述方式依次连接有多段高压反渗透装置,最后一段高压反渗透浓水箱收集的浓 水进入正渗透装置35进行处理,将废水含盐量浓缩至200000mg/L以上,得到浓盐水。
[0034] 根据本发明的一个具体实施例,正渗透装置35的汲取液为二氧化碳和氨水的溶 液,汲取液使用一段时间后被稀释,因此需要通过正渗透汲取液再生装置36对汲取液进行 再生,提高正渗透装置35的性能,减少资源的浪费。
[0035] 具体而言,预处理单元1包括依次连接的废水调节池11、一级反应箱12、沉淀箱13、 二级反应箱14、微滤浓缩箱15、微滤膜装置16和微滤产水箱17,废水调节池11中用于加入脱 硫废水,对脱硫废水进行初步的调节,然后脱硫废水进入沉淀箱I3中,沉淀箱13用于沉淀水 中的沉淀物,二级反应箱14用于降低水的硬度,微滤膜装置16对水进一步过滤处理,除去水 中的悬浮颗粒物,经过微滤膜装置16处理后的废水进入微滤产水箱I7,从而输送至深度处 理单元2中,预处理单元1将废水中的Ca2+、Mg2+、S〇42_含量降低至标准范围以内,实现了废水 的初步净化,且设备运行稳定可靠,净化效果良好。
[0036] 根据本发明的一个具体实施例,废水调节池11中设置有曝气搅拌装置,通过曝气 搅拌装置可将通入废水调节池H中的压缩空气更好地溶入脱硫废水中。曝气搅拌装置可以 实现:1)均质调节脱硫废水;2)部分去除C0D以及NH3-N的功能。
[0037] 根据本发明的一个具体实施例,深度处理单元2还包括超滤产水箱22、纳滤缓冲箱 26和纳滤产水箱28,超滤产水箱22与超滤装置21相连,纳滤缓冲箱26连接在膜脱氨装置25 和纳滤装置27之间,纳滤产水箱28连接在纳滤装置27的出水端,经过超滤装置21超滤处理 后的水进入超滤产水箱22中,然后进入臭氧催化氧化装置23中,然后又经过离子膜交换树 脂装置24和膜脱氨装置25处理后进入纳滤缓冲箱26中,进入纳滤缓冲箱26中的水通过水栗 栗入纳滤装置27中进行纳滤处理降低水中S〇42_的含量,经过纳滤处理后的水进入纳滤产水 箱28中,从而进入膜浓缩单元3中,深度处理单元2中的设备运行稳定,净化效果良好。
[0038] 如图2所示,一种脱硫废水零排放及资源化利用方法,包括以下步骤: S1,预处理,脱硫废水进入预处理单元1,对废水进行化学软化处理,除去废水中的沉 淀,分别将废水中的Ca2+、Mg2+、S〇42_浓度降低至20、15、1000 mg/L以下; S2,深度处理,经过S1处理后的脱硫废水进入深度处理单元2,将脱硫废水中的SS (悬浮 物)、C0D (化学需氧量)、硬度(以CaC03含量计算)、NH3-N和S〇42_的浓度分别降低至2、20、10、 l、100mg/L以下; S3,膜浓缩处理,经过S2处理后的渗透液经过膜浓缩单元3,依次经反渗透和正渗透作 用,将软化水的TDS含量浓缩至200000mg/L以上,得到浓盐水,提高废水的资源化利用率; S4,中水回用处理,将S3处理后的产水收集后经中水回用单元4,将产水中的TDS降低至 20mg/L,作为锅炉给水使用,实现零排放,保护环境; S5,水解离处理,将S3处理后的浓盐水经双极膜水解离单元5,得到资源化利用的氢氧 化钠溶液和盐酸溶液,提高废水的资源化利用率。
[0039] 具体而言,预处理的步骤依次包括:将脱硫废水加入废水调节池11中;向一级反应 箱12的脱硫废水中加入氢氧化钙和氯化钙,降低脱硫废水中的Mg2+和S042_浓度;向沉淀箱13 中加入絮凝剂;向二级反应箱14中加入氢氧化钠和碳酸钠,降低脱硫废水中硬度;最后通过 排污泵排出沉淀箱13中的污泥,该方法防止了设备结垢的现象。
[0040] 具体而言,深度处理的步骤包括:经过S1处理后的废水经超滤去除废水中悬浮物; 经过超滤作用后的渗透液经过超滤产水箱22,然后依次经过臭氧催化氧化、离子膜交换树 月旨、膜脱氨降低废水中⑶D、硬度和NH3-N的含量;然后通过高压水泵输送至纳滤装置 行纳滤作用将脱硫废水中的Cl—和S〇42—分开,得到主要含Cl—的渗透液和主要含SO/—的浓缩 液,含SO,的浓缩液回到预处理单元1的一级反应箱12中,从而进一步除去废水中S〇/的含 量,含cr的渗透液流至纳滤产水箱28中,然后进入膜浓缩单元3,从而进一步制成浓盐水, 用于工业,提高废水的资源化利用率。
[0041] 具体而言,膜浓缩处理过程包括:经过S2处理后的渗透液经过反渗透装置获得产 水和浓水,产水至中水回用单元4,浓水至正渗透装置35处理获得浓盐水。相对于现有技术 中的蒸发结晶的方法获得的副产盐来说,通过该方法获得的浓盐水品质更高,使用范围更 广,不需要投入蒸发结晶设备,减少了设备投入的浪费。
[0042] 根据本发明的一个具体实施例,多段高压反渗透装置处理后的产水和正渗透汲取 液再生过程中产生的再生水中仍然含有少量的TDS (杂质),将其进行汇总后进入中水回用 单元4的中水回用原水箱41中,经过低压反渗透装置42处理,产水中的TDS含量<2〇mg/L、 NH3-N含量<2mg/L、TOC含量<2mg/L,完全满足中水回用指标要求。经过低压反渗透装置42处 理后的浓水,回至第一段高压反渗透装置31的进水箱,从而进一步生产浓盐水。
[0043] 根据本发明的一个具体实施例,预处理单元1的废水调节池11中通入有压缩空气。
[0044] 以上实施例仅是为充分说明本发明而所举的较佳的实施例,本发明的保护范围不 限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换,均在本发明的保 护范围之内。本发明的保护范围以权利要求书为准。
Claims (10)
1. 一种脱硫废水零排放及资源化利用装置,其特征在于,包括: 预处理单元,用于降低脱硫废水中Ca2+、Mg2+和S04t的含量; 深度处理单元,用于降低脱硫废水中SS、COD、硬度、NH3-N和S〇42_的含量,所述深度处理 单元与所述预处理单元相连; 膜浓缩单元,用于得到浓盐水,所述膜浓缩单元与所述深度处理单元相连; 中水回用单元,用于收集中水,并降低中水中的TDS含量,所述中水回用单元与所述膜 浓缩单元相连; 和双极膜水解离单元,用于得到氢氧化钠溶液和盐酸溶液,所述双极膜水解离单元与 所述膜浓缩单元相连, 所述深度处理单元包括依次连接的超滤装置、臭氧催化氧化装置、离子膜交换树脂装 置、膜脱氨装置和纳滤装置; 所述膜浓缩单元包括依次连接的反渗透装置和正渗透装置; 所述水回用单元包括依次连接的中水回用原水箱和低压反渗透装置; 所述双极膜水解离单元包括依次连接的缓冲箱和双极膜水解离装置。
2. 根据权利要求1所述的一种脱硫废水零排放及资源化利用装置,其特征在于,所述反 渗透装置包括依次连接的多段高压反渗透装置以及对应的产水箱,每段高压反渗透装置的 浓水作为下一段高压反渗透装置的进水,多段高压反渗透装置的产水通过所述产水箱流至 所述中水回用单元,最后一段高压反渗透装置的浓水流至所述正渗透装置。
3. 根据权利要求1所述的一种脱硫废水零排放及资源化利用装置,其特征在于,所述预 处理单元包括依次连接的废水调节池、一级反应箱、沉淀箱、二级反应箱、微滤浓缩箱、微滤 膜装置和微滤产水箱。
4. 根据权利要求3所述的一种脱硫废水零排放及资源化利用装置,其特征在于,所述废 水调节池中设置有曝气搅拌装置。
5. 根据权利要求1所述的一种脱硫废水零排放及资源化利用装置,其特征在于,所述深 度处理单元还包括超滤产水箱、纳滤缓冲箱和纳滤产水箱,所述超滤产水箱与所述超滤装 置相连,所述纳滤缓冲箱连接在所述膜脱氨装置和纳滤装置之间,所述纳滤产水箱连接在 所述纳滤装置的出水端。
6. —种脱硫废水零排放及资源化利用方法,其特征在于,包括以下步骤: S1,预处理,脱硫废水进入预处理单元,对废水进行化学软化处理,除去废水中的沉淀, 分别将废水中的〇&2+、1%2+、3〇42_浓度降低至20、15、100〇11^凡以下; 52, 深度处理,经过S1处理后的脱硫废水进入深度处理单元,将脱硫废水中的SS、COD、 硬度、NH3-N和S〇42_的浓度分别降低至2、20、10、l、100mg/L以下; 53, 膜浓缩处理,经过S2处理后的渗透液经过膜浓缩单元,依次经反渗透和正渗透作 用,将软化水的TDS含量浓缩至2〇〇〇〇〇mg/L以上,得到浓盐水; 54, 中水回用处理,将S3处理后的产水收集后经中水回用单元,将产水中的TDS降低至 20mg/L,作为锅炉给水使用; S5,水解离处理,将S3处理后的浓盐水经双极膜水解离单元,得到资源化利用的氢氧化 钠溶液和盐酸溶液。
7. 根据权利要求6所述的一种脱硫废水零排放及资源化利用方法,其特征在于,所述预 处理的步骤依次包括:将脱硫废水加入废水调节池中;向一级反应箱的脱硫废水中加入氢 氧化钙和氯化钙,降低脱硫废水中的Mg2+和S〇42l度;向沉淀箱中加入絮凝剂;向二级反应 箱中加入氢氧化钠和碳酸钠,降低脱硫废水中硬度;最后通过排污泵排出所述沉淀箱中的 污泥。
8. 根据权利要求6所述的一种脱硫废水零排放及资源化利用方法,其特征在于,所述深 度处理的步骤包括:经过S1处理后的废水经超滤去除废水中悬浮物;然后依次经过臭氧催 化氧化、离子膜交换树脂、膜脱氨降低废水中COD、硬度和NH3-N的含量;然后进行纳滤作用 将脱硫废水中的cr和s〇42-分开,得到主要含cr的渗透液和主要含3〇42_的浓缩液,所述浓缩 液回到所述预处理单元,所述渗透液流至所述膜浓缩单元。
9. 根据权利要求6所述的一种脱硫废水零排放及资源化利用方法,其特征在于,所述膜 浓缩处理过程包括:经过S2处理后的渗透液经过高压反渗透装置获得产水和浓水,所述产 水至所述中水回用单元,所述浓水至正渗透装置处理获得浓盐水。
10. 根据权利要求6所述的一种脱硫废水零排放及资源化利用方法,其特征在于,所$ 预处理单元的废水调节池中通入有压缩空气。
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