CN105198141A - 一种高温高盐废水的零排放方法 - Google Patents
一种高温高盐废水的零排放方法 Download PDFInfo
- Publication number
- CN105198141A CN105198141A CN201410250381.9A CN201410250381A CN105198141A CN 105198141 A CN105198141 A CN 105198141A CN 201410250381 A CN201410250381 A CN 201410250381A CN 105198141 A CN105198141 A CN 105198141A
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- water
- temperature
- nanofiltration
- waste water
- membrane
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- 239000002351 wastewater Substances 0.000 title claims abstract description 161
- 238000007599 discharging Methods 0.000 title abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 207
- 238000001728 nano-filtration Methods 0.000 claims abstract description 194
- 239000012528 membrane Substances 0.000 claims abstract description 193
- 238000004821 distillation Methods 0.000 claims abstract description 135
- 238000000034 method Methods 0.000 claims abstract description 128
- 239000011780 sodium chloride Substances 0.000 claims abstract description 117
- 150000003839 salts Chemical class 0.000 claims abstract description 107
- 238000002425 crystallisation Methods 0.000 claims abstract description 58
- 230000005712 crystallization Effects 0.000 claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000002500 ions Chemical class 0.000 claims abstract description 21
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical group 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[Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound 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- 239000002244 precipitate Substances 0.000 claims description 15
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- 239000012141 concentrate Substances 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound 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[Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012466 permeate Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000012510 hollow fiber Substances 0.000 claims description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N Tetrafluoroethylene Chemical group 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FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
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- 238000000108 ultra-filtration Methods 0.000 description 2
- UEJWRQDKIBEMCR-UHFFFAOYSA-L calcium;sodium;carbonate Chemical compound 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Abstract
本发明涉及一种高温高盐废水的零排放方法,先采用耐高温纳滤膜去除废水中的多价离子和少量有机物,之后采用膜蒸馏技术对废水进行深度浓缩处理,膜蒸馏浓水再进行蒸发结晶处理,将膜蒸馏浓水中的盐类结晶出来,集中干化处置。处理过程中产生的纳滤浓水加盐进行沉淀处理,得到钙渣,集中干化处置,沉淀处理后产生的上清液进行活性炭吸附,活性炭吸附后的产水和纳滤进水混合进入纳滤单元循环处理。膜蒸馏产水以及蒸发结晶产水均可回用于生产工艺。本发明所述的高温高盐废水的零排放方法,在实现该类废水零排放的同时,有效利用了废水自身余热,降低了整个工艺流程的能耗,实现了废水资源化和能源化的高效利用,具有显著社会效益和环境效益。
Description
技术领域
[0001] 本发明涉及利用膜分离技术处理高温高盐废水,具体说是一种高温高盐废水的零排放方法。尤指利用“纳滤+膜蒸馏+蒸发结晶”处理高温高盐废水的零排放方法。
背景技术
[0002] 近年来,石化企业产生的高盐废水成为一个处理难题,有的高盐废水还带有一定温度,该类废水如果直接排放,不仅带来盐对生态环境的严重污染,并且也造成极大的能源浪费。因此,亟需寻求新型的分离技术解决该类废水的处理排放问题。
[0003] 纳滤(NF)是介于超滤与反渗透之间的一种膜分离技术,其截留分子量在200〜1000范围内,孔径为几纳米。纳滤具有以下技术特点:能截留分子量大于100的有机物以及多价离子,允许小分子有机物和单价离子透过;可在高温、酸、碱等苛刻条件下运行,耐污染;运行压力低,膜通量高,装置运行费用低;纳滤对于不同价态的阴离子存在道南效应。物料的荷电性、离子价数和浓度对膜的分离效应有很大影响。与超滤或反渗透相比,纳滤过程对单价离子和分子量低于200的有机物截留较差,而对二价或多价离子及分子量介于200〜500之间的有机物有较高脱除率。基于这一特性,纳滤过程主要应用于水的软化、净化以及相对分子质量在百级的物质的分离、分级和浓缩、脱色和去异味等。在实际废水处理中,可以将纳滤和其他污水处理过程相结合,以进一步降低费用和提高处理效果。
[0004] 膜蒸馏(MD)由于能够脱除更高浓度的盐分以及更高的脱盐率而逐渐受到各国专家重视并展开了广泛研究,它可以算是迄今为止脱盐效率最高的膜技术,脱盐率高达99%以上。膜蒸馏是采用微孔疏水膜,以膜两侧蒸汽压差为驱动力的一种新型膜分离过程。膜蒸馏所用的膜为不被待处理溶液润湿的疏水微孔膜,即只有蒸汽能够进入膜孔,液体不能透过膜孔。膜蒸馏的优势主要是:产水水质好,脱盐率高,水回收率高,可利用工业废热。和多效蒸发相比,膜蒸馏可以低温操作,产水水质更好,蒸馏效率更高,不存在蒸发塔的结垢和腐蚀问题,设备造价也比常规蒸馏塔低;和反渗透相比,膜蒸馏可常压运行,对预处理要求低,可处理反渗透不能处理的高盐废水,水回收率更高。
[0005] 中国专利CN101928087涉及一种高盐废水的处理方法,该方法采用“调碱除硬+浸没式微滤+中和+膜蒸馏”的处理流程。该专利所处理废水的电导率范围为3000〜ΙΟΟΟΟμ s/cm,总硬度1000〜3000mg/L,采用该处理流程处理专利中所述废水,对高盐废水进行了深度浓缩的同时,得到了膜蒸馏产水。中国专利CN102936065也涉及一种处理废水的方法,该方法也采用加碱除硬+过滤+真空膜蒸馏的工艺流程,处理的废水体系为电导率10000-50000 μ s/cm,总硬度600_1800mg/L的废水,该股废水的电导率较高。该股废水采用氢氧化钠和碳酸钠去除废水中的硬度。上述两个专利对于膜蒸馏的浓水问题并没有给出处理方法,由此给生态环境带来了新的困扰。
发明内容
[0006] 针对现有技术中存在的缺陷,本发明的目的在于提供一种高温高盐废水的零排放方法,在实现该类废水零排放的同时,有效利用了废水自身余热,降低了整个工艺流程的能耗,实现了废水资源化和能源化的高效利用,具有显著社会效益和环境效益。
[0007] 为达到以上目的,本发明采取的技术方案是:
[0008] 一种高温高盐废水的零排放方法,其特征在于:首先采用耐高温纳滤膜去除高温高盐废水中的多价离子和少量有机物,之后采用膜蒸馏技术对去除硬度和部分有机物后的高温高盐废水进行深度浓缩处理,经过膜蒸馏深度浓缩处理后的膜蒸馏浓水再进行蒸发结晶处理,将膜蒸馏浓水中的盐类结晶出来,集中干化处置。
[0009] 在上述技术方案的基础上,纳滤处理过程中产生的纳滤浓水加盐进行沉淀处理,得到钙渣,集中干化处置,沉淀后的上清液进行活性炭吸附,活性炭吸附后的产水和纳滤进水混合进入纳滤单元循环处理。
[0010] 在上述技术方案的基础上,膜蒸馏处理过程中产生的膜蒸馏产水以及蒸发结晶处理过程中产生的蒸发结晶产水均可回用于生产工艺。
[0011] 在上述技术方案的基础上,具体包括以下步骤:
[0012] (I)纳滤;将所述具有一定温度的高温高盐废水进入到纳滤单元进行纳滤过滤处理,去除高温高盐废水中的硬度等多价离子和少量有机物;
[0013] 经过纳滤单元分离浓缩后,得到纳滤产水和纳滤浓水,其中纳滤产水进入步骤(2)进行膜蒸馏处理;
[0014] (2)膜蒸馏;将步骤(I)中经过纳滤单元去除硬度等多价离子后的纳滤产水,进行调酸处理,之后进入膜蒸馏单元进行深度浓缩处理;
[0015] 经过膜蒸馏单元分离浓缩后,得到膜蒸馏产水和膜蒸馏浓水;
[0016] (3)蒸发结晶;将步骤(2)中经过膜蒸馏深度浓缩后的膜蒸馏浓水进入蒸发结晶单元进行蒸发结晶处理,得到盐类晶体和蒸发结晶产水。
[0017] 在上述技术方案的基础上,纳滤浓水中加入盐类将钙离子沉淀下来得到钙渣,集中干化处置;
[0018] 经过钙离子沉淀后的纳滤浓水的上清液直接返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理,或上清液先进入活性炭吸附单元进行活性炭吸附后再返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理。
[0019] 在上述技术方案的基础上,吸附饱和后的活性炭进行再生或作为燃料直接进行燃烧处理。
[0020] 在上述技术方案的基础上,所述纳滤进水即高温高盐废水,其水质特征为:废水温度 60 〜80 °C,废水 ρΗ6.5 〜7.5,电导率 10000 〜20000 μ s/cm, CODcrO 〜100mg/L,Na+2000 〜4000mg/L, Cl 2500 〜5000mg/L,以 CaCO3 计总硬度 1000 〜3000mg/L。
[0021] 在上述技术方案的基础上,纳滤单元中的纳滤膜组件采用耐高温纳滤膜组件,膜材料为聚酰胺。
[0022] 在上述技术方案的基础上,纳滤单元的操作条件为:进料液侧操作压力0.3〜1.0MPa0
[0023] 在上述技术方案的基础上,向纳滤浓水中加入的盐类为硫酸钠或碳酸钠或两者的混合物,盐类的投加量为Ca2+:盐的摩尔比为1:1 ;
[0024] 添加两者的混合物时,硫酸钠、碳酸钠的配比任意。
[0025] 在上述技术方案的基础上,经过钙渣沉淀后的纳滤浓水的上清液,在废水中不含COD时,直接返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理;
[0026] 在废水中含有COD时,则先进入活性炭吸附单元进行活性炭吸附后再返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理。
[0027] 在上述技术方案的基础上,所述的活性炭为粉末活性炭或颗粒活性炭,投加量为活性炭=COD的质量比为2:1〜10:1。
[0028] 在上述技术方案的基础上,所述的调酸处理所用的酸为盐酸;
[0029] 调酸处理为将纳滤产水的pH调节到6.0〜6.5。
[0030] 在上述技术方案的基础上,所述膜蒸馏单元的操作条件为:进料液侧废水PH6.0〜6.5,进料液侧废水温度60°C〜80°C,进料液侧膜面流速0.6〜1.2m/s,渗透液侧真空度-0.075 〜-0.095MPa。
[0031] 在上述技术方案的基础上,所述膜蒸馏单元的膜蒸馏组件的膜材料为聚偏氟乙烯、聚四氟乙烯或聚丙烯;膜孔径范围为0.15 μ m〜0.2 μ m ;
[0032] 所述的膜蒸馏组件形式为中空纤维式或板式;
[0033] 所述的膜蒸馏组件为一组或多组串联或并联;
[0034] 所述膜蒸馏单元的膜蒸馏形式为内压式真空膜蒸馏。
[0035] 在上述技术方案的基础上,所述蒸发结晶单元采用现有市售蒸发结晶器,热源采用废蒸汽加热。
[0036] 在上述技术方案的基础上,所述高温高盐废水经过纳滤单元循环处理,水回收率闻于85 % ;
[0037] 所述高温高盐废水经过膜蒸馏单元处理,水回收率高于90%。
[0038] 在上述技术方案的基础上,处理后的高温高盐废水,产水电导率< 300μ S/cm,产水C0D„〈10mg/L,产水T0C〈3mg/L,整个系统水回收率高于90%
[0039] 本发明所述的高温高盐废水的零排放方法,在实现该类废水零排放的同时,有效利用了废水自身余热,降低了整个工艺流程的能耗,实现了废水资源化和能源化的高效利用,具有显著社会效益和环境效益。
[0040] 采用本发明的方法处理高温高盐废水,在解决该股废水排放难题的同时,最大限度地回收了水资源,并有效利用了废水自身余热,基本实现了高温高盐废水的零排放,实现了废水资源化和能源化的高效利用。
附图说明
[0041] 本发明有如下附图:
[0042] 图1本发明的处理流程示意图。
具体实施方式
[0043] 以下结合附图对本发明作进一步详细说明。
[0044] 本发明所述的高温高盐废水的零排放方法,针对的是各类具有一定温度的高盐废水。针对本发明中待处理废水的水质特点,本发明采用“纳滤+膜蒸馏+蒸发结晶”的工艺流程,工艺流程中涉及的纳滤采用耐高温纳滤膜,主要用于去除待处理废水中的钙镁离子硬度。本发明所述的工艺流程在实现该类废水零排放的同时,有效利用了废水自身余热,降低了整个工艺流程的能耗,实现了废水资源化和能源化的高效利用,具有显著社会效益和环境效益。
[0045] 如图1所示,本发明所述的高温高盐废水的零排放方法,首先采用耐高温纳滤膜去除高温高盐废水中的多价离子(硬度等多价离子)和少量有机物,之后采用膜蒸馏技术对去除硬度和部分有机物后的高温高盐废水进行深度浓缩处理,经过膜蒸馏深度浓缩处理后的膜蒸馏浓水再进行蒸发结晶处理,将膜蒸馏浓水中的盐类结晶出来,集中干化处置。纳滤处理过程中产生的纳滤浓水送入沉淀池并加盐进行沉淀处理,得到钙渣,集中干化处置,沉淀后的上清液进行活性炭吸附,活性炭吸附后的产水和纳滤进水(即待处理的高温高盐废水)混合进入纳滤单元循环处理。膜蒸馏处理过程中产生的膜蒸馏产水以及蒸发结晶处理过程中产生的蒸发结晶产水均可回用于生产工艺。
[0046] 本发明所述的高温高盐废水的零排放方法,具体包括以下步骤:
[0047] (I)纳滤;将所述具有一定温度的高温高盐废水进入到纳滤单元进行纳滤过滤处理,去除高温高盐废水中的硬度等多价离子和少量有机物;
[0048] 经过纳滤单元分离浓缩后,得到纳滤产水和纳滤浓水,其中纳滤产水进入步骤(2)进行膜蒸馏处理;
[0049] 纳滤浓水中加入盐类将钙离子沉淀下来得到钙渣,集中干化处置,经过钙离子沉淀后的纳滤浓水的上清液直接返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理,或上清液先进入活性炭吸附单元进行活性炭吸附后再返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理;
[0050] (2)膜蒸馏;将步骤(I)中经过纳滤单元去除硬度等多价离子后的纳滤产水,进行调酸处理,之后进入膜蒸馏单元进行深度浓缩处理;经过膜蒸馏单元分离浓缩后,得到膜蒸馏产水和膜蒸馏浓水;
[0051] (3)蒸发结晶;将步骤(2)中经过膜蒸馏深度浓缩后的膜蒸馏浓水进入蒸发结晶单元进行蒸发结晶处理,得到盐类晶体(结晶盐类)和蒸发结晶产水。
[0052] 在上述技术方案的基础上,步骤(I)中吸附饱和后的活性炭进行再生或作为燃料直接进行燃烧处理。
[0053] 在上述技术方案的基础上,步骤(2)中产生的膜蒸馏产水以及步骤(3)中产生的蒸发结晶产水均可回用于生产工艺。
[0054] 在上述技术方案的基础上,所述纳滤进水即待处理的高温高盐废水,其水质特征为:废水温度 60 〜80°C,废水 ρΗ6.5 〜7.5,电导率 10000 〜20000 μ s/cm, CODcrO 〜10mg/L, Na+2000 〜4000mg/L, Cl 2500 〜5000mg/L,总硬度(CaCO3) 1000 〜3000mg/L。
[0055] 在上述技术方案的基础上,纳滤单元中的纳滤膜组件采用耐高温纳滤膜组件,如陶氏、GE或科氏耐高温纳滤膜组件,膜材料为聚酰胺。
[0056] 在上述技术方案的基础上,纳滤单元的操作条件为:进料液侧操作压力0.3〜1.0MPa0
[0057] 在上述技术方案的基础上,向纳滤浓水中加入的盐类为硫酸钠或碳酸钠或两者的混合物,盐类的投加量为Ca2+:盐的摩尔比为1:1 ;
[0058] 添加两者的混合物时,硫酸钠、碳酸钠的配比任意。
[0059] 在上述技术方案的基础上,经过钙渣沉淀后的纳滤浓水的上清液,在废水中不含COD时,直接返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理;
[0060] 在废水中含有COD时,则先进入活性炭吸附单元进行活性炭吸附后再返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理。
[0061] 在上述技术方案的基础上,所述的活性炭为粉末活性炭或颗粒活性炭,投加量为活性炭=COD的质量比为2:1〜10:1。
[0062] 在上述技术方案的基础上,所述的调酸处理所用的酸为盐酸;
[0063] 调酸处理为将纳滤产水的pH调节到6.0〜6.5。
[0064] 在上述技术方案的基础上,所述膜蒸馏单元的操作条件为:进料液侧废水PH6.0〜6.5,进料液侧废水温度60°C〜80°C,进料液侧膜面流速0.6〜1.2m/s,渗透液侧真空度-0.075 〜-0.095MPa。
[0065] 在上述技术方案的基础上,所述膜蒸馏单元的膜蒸馏组件的膜材料为聚偏氟乙烯、聚四氟乙烯或聚丙烯;膜孔径范围为0.15 μ m〜0.2 μ m ;
[0066] 所述的膜蒸馏组件形式为中空纤维式或板式;
[0067] 所述的膜蒸馏组件为一组或多组串联或并联;
[0068] 所述膜蒸馏单元的膜蒸馏形式为内压式真空膜蒸馏。
[0069] 在上述技术方案的基础上,所述蒸发结晶单元采用现有市售蒸发结晶器,热源采用废蒸汽加热。
[0070] 在上述技术方案的基础上,所述高温高盐废水经过纳滤单元循环处理,水回收率闻于85 % ;
[0071] 所述高温高盐废水经过膜蒸馏单元处理,水回收率高于90%。
[0072] 本发明与现有技术的实质性区别在于,针对现有技术中对高温高盐废水的难于处理问题,采用“纳滤+膜蒸馏+蒸发结晶”处理高温高盐废水。首先,采用耐高温纳滤膜去除高温高盐废水中的硬度等多价离子和少量有机物,之后采用膜蒸馏技术对去除硬度和部分有机物后的高温高盐废水进行深度浓缩处理,经过膜蒸馏深度浓缩处理后的膜蒸馏浓水再进行蒸发结晶处理,将浓水中的盐类结晶出来,集中干化处置。该处理过程中产生的纳滤浓水加盐进行沉淀处理,得到钙渣,沉淀后的上清液进行活性炭吸附,活性炭吸附后的产水和纳滤进水混合进入纳滤单元循环处理。通过上述工艺流程,在解决该股废水排放难题的同时,最大限度地回收了水资源,并有效利用了废水自身余热,基本实现了高温高盐废水的零排放。
[0073] 本发明的有益效果是:
[0074] 1、本发明针对高温高盐废水,在采用耐高温纳滤膜去除高温高盐废水中的硬度等多价离子的基础上,通过膜蒸馏技术和蒸发结晶技术深度浓缩处理,最大限度的回收了水资源,并有效利用了废水自身余热,解决了高温高盐废水的深度处理甚至零排放问题,实现了废水资源化和能源化的高效利用;
[0075] 2、本发明充分利用了纳滤去除硬度等多价离子的优势,去除高温高盐废水中的硬度,便于后续膜蒸馏处理;
[0076] 3、本发明中的纳滤工艺有效降低了膜蒸馏过程的膜污染,提高了膜蒸馏深度浓缩系统的回收率;
[0077] 4、本发明中的膜蒸馏过程不需要外加压力或外压压力很小,方法简单易行,容易操作;
[0078] 5、本发明中的膜蒸馏过程的膜污染较轻,延长了该过程的连续稳定运行时间;
[0079] 6、采用本发明的方法,不仅可以获得大量满足回用需求的产水,同时也解决了高温高盐废水的难以处理问题,在最大限度回收水资源的同时,基本实现零排放,具有重要环境效益;
[0080] 7、本发明的方法有效整合了各自的技术优势,有效利用了废水自身余热,优化了高温高盐废水深度处理回用的工艺流程。本发明的方法相对于废水直接进行多效蒸发而言,运行费用低,并有效减少了结垢和有机物的污染;
[0081] 经过本发明方法处理后的高温高盐废水,产水电导率彡300 μ S/cm,产水CODraX 10mg/L,产水T0C〈3mg/L,整个系统水回收率高于90%。
[0082] 以下为具体实施例。
[0083] 实施例1
[0084] 工艺流程示意图见图1。图中高温高盐废水的水质特征为:废水温度60°C,废水pH6.5,电导率 10000 μ s/cm, C0Dcr0mg/L, Na+2000mg/L, Cl 2500mg/L,总硬度(CaCO3) 100mg/L0
[0085] 步骤如下:
[0086] (I)纳滤。将所述具有一定温度的高温高盐废水进入到纳滤单元进行纳滤处理,去除高温高盐废水中的硬度等多价离子和少量有机物。
[0087] 经过纳滤单元分离浓缩后,纳滤产水进入步骤(2)进行处理,纳滤浓水中加入碳酸钠将钙离子沉淀下来得到钙渣,集中干化处置,碳酸钠的投加量为Ca2+:碳酸钠的摩尔比为1:1,经过钙离子沉淀后的纳滤浓水的上清液返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理;
[0088] (2)膜蒸馏。将步骤⑴中的纳滤产水,采用盐酸将pH调节到6,之后进入膜蒸馏单元进行深度浓缩处理。经过膜蒸馏单元分离浓缩后,得到膜蒸馏产水和膜蒸馏浓水;
[0089] (3)蒸发结晶。将步骤(2)中经过膜蒸馏深度浓缩后的剩余膜蒸馏浓水进入蒸发结晶单元进行蒸发结晶处理,蒸发热源采用废蒸汽加热,经过蒸发结晶单元蒸发结晶后,得到盐类晶体和蒸发结晶产水。
[0090] 上述步骤中,步骤(I)的纳滤膜组件采用耐高温聚酰胺纳滤膜组件;
[0091] 上述步骤中,步骤(I)的纳滤单元的操作条件为:进料液侧操作压力0.3MPa ;
[0092] 在上述纳滤单元的运行条件下,纳滤出水硬度基本在70mg/L左右;
[0093] 上述步骤中,步骤(I)中经过加入碳酸钠沉淀后的上清液出水硬度小于15mg/L ;
[0094] 上述步骤中,所用膜蒸馏组件采用聚四氟乙烯(PTFE)中空纤维疏水膜组件,膜孔径为0.2 μ m,膜蒸馏形式为内压式真空膜蒸馏。
[0095] 运行过程中,膜蒸馏单元的操作条件为:进料液侧废水pH6,进料液侧废水温度60°C,进料液侧膜面流速1.2m/s,渗透液侧真空度-0.095MPa ;
[0096] 在上述纳滤单元的操作条件下,纳滤膜通量保持在60〜70L/m2 *h,水回收率高于85% ;
[0097] 在上述膜蒸懼单元的操作条件下,膜蒸懼膜通量保持在2.5〜3.5L/m2 *h,水回收率闻于90 % ;
[0098] 上述步骤中,步骤(2)中产生的膜蒸馏产水以及步骤(3)中产生的蒸发结晶产水均可回用于生产工艺;
[0099] 上述步骤中,膜蒸馏浓水经过步骤(3)的蒸发结晶单元蒸发结晶处理,得到盐类晶体,集中干化处置;
[0100] 经过本发明方法处理后的高温高盐废水,系统产水电导率<300yS/cm,产水CODraX 10mg/L,产水T0C〈3mg/L,整个系统水回收率高于85%。
[0101] 实施例2
[0102] 工艺流程示意图见图1。图中高温高盐废水的水质特征为:废水温度70°C,废水pH7,电导率 15000 μ s/cm, C0Dcr50mg/L, Na+3000mg/L, Cl 3500mg/L,总硬度(CaCO3) 2000mg/L0
[0103] 实施例2的操作步骤与实施例1相同。其中,与实施例1不同的是,纳滤浓水中加入的是硫酸钠用于将钙离子沉淀下来,硫酸钠的投加量为Ca2+:硫酸钠的摩尔比为1:1 ;经过钙离子沉淀后的纳滤浓水的上清液采用颗粒活性炭进行活性炭吸附,颗粒活性炭的投加量为颗粒活性炭:C0D的质量比为10:1 ;纳滤产水采用盐酸将pH调节到6.5,之后进入膜蒸馏单元进行深度浓缩处理。
[0104] 上述步骤中,步骤(I)的纳滤膜组件采用耐高温聚酰胺纳滤膜组件;
[0105] 上述步骤中,步骤(I)的纳滤单元的操作条件为:进料液侧操作压力0.5MPa ;
[0106] 在上述纳滤单元的运行条件下,纳滤出水硬度基本在80mg/L左右;
[0107] 上述步骤中,步骤(I)中经过加入硫酸钠沉淀后的上清液出水硬度小于20mg/L ;
[0108] 上述步骤中,步骤(I)中经过颗粒活性炭吸附后的出水CODct小于10mg/L,TOC小于 3mg/L ;
[0109] 上述步骤中,所用膜蒸馏组件采用聚四氟乙烯(PTFE)中空纤维疏水膜组件,膜孔径为0.2 μ m,膜蒸馏形式为内压式真空膜蒸馏。
[0110] 运行过程中,膜蒸馏单元的操作条件为:进料液侧废水pH6.5,进料液侧废水温度70 0C,进料液侧膜面流速0.8m/s,渗透液侧真空度-0.085MPa ;
[0111] 在上述纳滤单元的操作条件下,纳滤膜通量保持在90〜105L/m2.h,水回收率高于 85% ;
[0112] 在上述膜蒸馏单元的操作条件下,膜蒸馏膜通量保持在4〜6L/m2 *h,水回收率高于 90% ;
[0113] 上述步骤中,步骤(2)中产生的膜蒸馏产水以及步骤(3)中产生的蒸发结晶产水均可回用于生产工艺;步骤(I)中吸附饱和后的活性炭进行再生处理;
[0114] 上述步骤中,膜蒸馏浓水经过步骤(3)的蒸发结晶单元蒸发结晶处理,得到盐类晶体,集中干化处置;
[0115] 经过本发明方法处理后的高温高盐废水,系统产水电导率< 300 μ S/cm,产水CODraX 10mg/L,产水T0C〈3mg/L,整个系统水回收率高于85%。
[0116] 实施例3
[0117] 工艺流程示意图见图1。图中高温高盐废水的水质特征为:废水温度80°C,废水 ρΗ7.5,电导率 20000 μ s/cm, C0Dcr80mg/L, Na+4000mg/L, Cl 5000mg/L,总硬度(CaCO3) 3000mg/L ο
[0118] 实施例3的操作步骤与实施例1相同。其中,与实施例1不同的是,纳滤浓水中加入的是碳酸钠和硫酸钠的混合物用于将钙离子沉淀下来,碳酸钠和硫酸钠的混合物投加量为Ca2+:(碳酸钠+硫酸钠)的摩尔比为1:1 ;经过钙离子沉淀后的纳滤浓水的上清液采用粉末活性炭进行活性炭吸附,粉末活性炭的投加量为粉末活性炭=COD的质量比为2:1 ;纳滤产水采用盐酸将PH调节到6.5,之后进入膜蒸馏单元进行深度浓缩处理。
[0119] 上述步骤中,步骤(I)的纳滤膜组件采用耐高温聚酰胺纳滤膜组件;
[0120] 上述步骤中,步骤(I)的纳滤单元的操作条件为:进料液侧操作压力0.7MPa ;
[0121] 在上述纳滤单元的运行条件下,纳滤出水硬度基本在90mg/L左右;
[0122] 上述步骤中,步骤(I)中经过加入碳酸钠和硫酸钠沉淀后的上清液出水硬度小于15mg/L ;
[0123] 上述步骤中,步骤⑴中经过粉末活性炭吸附后的出水CODct小于10mg/L,TOC小于 3mg/L ;
[0124] 上述步骤中,所用膜蒸馏组件为聚丙烯(PP)中空纤维疏水膜组件,膜孔径为0.15 μ m,膜蒸馏形式为内压式真空膜蒸馏。
[0125] 运行过程中,膜蒸馏单元的操作条件为:进料液侧废水pH6.5,进料液侧废水温度80°C,进料液侧膜面流速1.0m/s,渗透液侧真空度-0.075MPa ;
[0126] 在上述纳滤单元的操作条件下,纳滤膜通量保持在130〜150L/m2.1ι,水回收率高于 85% ;
[0127] 在上述膜蒸馏单元的操作条件下,膜蒸馏膜通量保持在5〜7L/m2 *h,水回收率高于 90% ;
[0128] 上述步骤中,步骤(2)中产生的膜蒸馏产水以及步骤(3)中产生的蒸发结晶产水均可回用于生产工艺;步骤(I)中吸附饱和后的活性炭可作为燃料直接进行燃烧处理;
[0129] 上述步骤中,膜蒸馏浓水经过步骤(3)的蒸发结晶单元蒸发结晶处理,得到盐类晶体,集中干化处置;
[0130] 经过本发明方法处理后的高温高盐废水,系统产水电导率< 300 μ S/cm,产水CODraX 10mg/L,产水T0C〈3mg/L,整个系统水回收率高于85%。
[0131] 实施例4
[0132] 工艺流程示意图见图1。图中高温高盐废水的水质特征为:废水温度80°C,废水 ρΗ7.5,电导率 20000 μ s/cm, C0Dcr100mg/L, Na+4000mg/L, Cl 5000mg/L,总硬度(CaCO3) 3000mg/L ο
[0133] 实施例4的操作步骤与实施例1相同。其中,与实施例1不同的是,纳滤浓水中加入的是碳酸钠,用于将钙离子沉淀下来,碳酸钠的投加量为Ca2+:碳酸钠的摩尔比为1:1 ;经过钙离子沉淀后的纳滤浓水的上清液采用粉末活性炭进行活性炭吸附,粉末活性炭的投加量为粉末活性炭=COD的质量比为5:1 ;纳滤产水采用盐酸将pH调节到6.5,之后进入膜蒸馏单元进行深度浓缩处理。
[0134] 上述步骤中,步骤(I)的纳滤膜组件采用耐高温聚酰胺纳滤膜组件;
[0135] 上述步骤中,步骤(I)的纳滤单元的操作条件为:进料液侧操作压力1.0MPa ;
[0136] 在上述纳滤单元的运行条件下,纳滤出水硬度基本在100mg/L左右;
[0137] 上述步骤中,步骤(I)中经过加入碳酸钠沉淀后的上清液出水硬度小于15mg/L ;
[0138] 上述步骤中,步骤⑴中经过粉末活性炭吸附后的出水CODct小于10mg/L,TOC小于 3mg/L ;
[0139] 上述步骤中,所用膜蒸馏组件为聚丙烯(PP)中空纤维疏水膜组件,膜孔径为0.2 μ m,膜蒸馏形式为内压式真空膜蒸馏。
[0140] 运行过程中,膜蒸馏单元的操作条件为:进料液侧废水pH6.5,进料液侧废水温度80 0C,进料液侧膜面流速0.6m/s,渗透液侧真空度-0.09MPa ;
[0141] 在上述纳滤单元的操作条件下,纳滤膜通量保持在170〜200L/m2.1ι,水回收率高于 85% ;
[0142] 在上述膜蒸馏单元的操作条件下,膜蒸馏膜通量保持在6〜9L/m2 *h,水回收率高于 90% ;
[0143] 上述步骤中,步骤(2)中产生的膜蒸馏产水以及步骤(3)中产生的蒸发结晶产水均可回用于生产工艺;步骤(I)中吸附饱和后的活性炭可作为燃料直接进行燃烧处理;
[0144] 上述步骤中,膜蒸馏浓水经过步骤(3)的蒸发结晶单元蒸发结晶处理,得到盐类晶体,集中干化处置;
[0145] 经过本发明方法处理后的高温高盐废水,系统产水电导率<300yS/cm,产水CODraX 10mg/L,产水T0C〈3mg/L,整个系统水回收率高于85%。
[0146] 实施例5
[0147] 工艺流程示意图见图1。图中高温高盐废水的水质特征为:废水温度75°C,废水pH6.5,电导率 10000 μ s/cm, C0Dcr0mg/L, Na+2000mg/L, Cl 2500mg/L,总硬度(CaCO3) 100mg/
L-1 O
[0148] 实施例5的操作步骤与实施例1相同。其中,与实施例1不同的是,纳滤浓水中加入的是碳酸钠,用于将钙离子沉淀下来,碳酸钠的投加量为Ca2+:碳酸钠的摩尔比为1:1 ;纳滤产水直接进入膜蒸馏单元进行深度浓缩处理。
[0149] 上述步骤中,步骤(I)的纳滤膜组件采用耐高温聚酰胺纳滤膜组件;
[0150] 上述步骤中,步骤(I)的纳滤单元的操作条件为:进料液侧操作压力0.5MPa ;
[0151] 在上述纳滤单元的运行条件下,纳滤出水硬度基本在70mg/L左右;
[0152] 上述步骤中,步骤(I)中经过加入碳酸钠沉淀后的上清液出水硬度小于15mg/L ;
[0153] 在上述纳滤单元的运行条件下,纳滤出水硬度基本在70mg/L左右;
[0154] 上述步骤中,所用膜蒸馏组件为聚四氟乙烯(PTFE)板式疏水膜组件,膜孔径为0.18 μ m,膜蒸馏形式为内压式真空膜蒸馏。
[0155] 运行过程中,膜蒸馏单元的操作条件为:进料液侧废水pH6.5,进料液侧废水温度75 0C,进料液侧膜面流速0.9m/s,渗透液侧真空度-0.09MPa ;
[0156] 在上述纳滤单元的操作条件下,纳滤膜通量保持在70〜80L/m2.1ι,水回收率高于85% ;
[0157] 在上述膜蒸馏单元的操作条件下,膜蒸馏膜通量保持在7〜10L/m2.h,水回收率闻于90 % ;
[0158] 上述步骤中,步骤(2)中产生的膜蒸馏产水以及步骤(3)中产生的蒸发结晶产水均可回用于生产工艺;
[0159] 上述步骤中,膜蒸馏浓水经过步骤(3)的蒸发结晶单元蒸发结晶处理,得到盐类晶体,集中干化处置;
[0160] 经过本发明方法处理后的高温高盐废水,系统产水电导率< 300 μ S/cm,产水CODraX 10mg/L,产水T0C〈3mg/L,整个系统水回收率高于85%。
[0161] 本说明书中未作详细描述的内容属于本领域专业技术人员公知的现有技术。
Claims (18)
1.一种高温高盐废水的零排放方法,其特征在于:首先采用耐高温纳滤膜去除高温高盐废水中的多价离子和少量有机物,之后采用膜蒸馏技术对去除硬度和部分有机物后的高温高盐废水进行深度浓缩处理,经过膜蒸馏深度浓缩处理后的膜蒸馏浓水再进行蒸发结晶处理,将膜蒸馏浓水中的盐类结晶出来,集中干化处置。
2.如权利要求1所述的高温高盐废水的零排放方法,其特征在于:纳滤处理过程中产生的纳滤浓水加盐进行沉淀处理,得到钙渣,集中干化处置,沉淀后的上清液进行活性炭吸附,活性炭吸附后的产水和纳滤进水混合进入纳滤单元循环处理。
3.如权利要求1所述的高温高盐废水的零排放方法,其特征在于:膜蒸馏处理过程中产生的膜蒸馏产水以及蒸发结晶处理过程中产生的蒸发结晶产水均可回用于生产工艺。
4.如权利要求1所述的高温高盐废水的零排放方法,其特征在于,具体包括以下步骤: (1)纳滤;将所述具有一定温度的高温高盐废水进入到纳滤单元进行纳滤过滤处理,去除高温高盐废水中的硬度等多价离子和少量有机物; 经过纳滤单元分离浓缩后,得到纳滤产水和纳滤浓水,其中纳滤产水进入步骤(2)进行膜蒸馏处理; (2)膜蒸馏;将步骤(I)中经过纳滤单元去除硬度等多价离子后的纳滤产水,进行调酸处理,之后进入膜蒸馏单元进行深度浓缩处理; 经过膜蒸馏单元分离浓缩后,得到膜蒸馏产水和膜蒸馏浓水; (3)蒸发结晶;将步骤(2)中经过膜蒸馏深度浓缩后的膜蒸馏浓水进入蒸发结晶单元进行蒸发结晶处理,得到盐类晶体和蒸发结晶产水。
5.如权利要求4所述的高温高盐废水的零排放方法,其特征在于:纳滤浓水中加入盐类将钙离子沉淀下来得到钙渣,集中干化处置; 经过钙离子沉淀后的纳滤浓水的上清液直接返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理,或上清液先进入活性炭吸附单元进行活性炭吸附后再返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理。
6.如权利要求5所述的高温高盐废水的零排放方法,其特征在于:吸附饱和后的活性炭进行再生或作为燃料直接进行燃烧处理。
7.如权利要求1或4所述的高温高盐废水的零排放方法,其特征在于:所述纳滤进水即高温高盐废水,其水质特征为:废水温度60〜80°C,废水pH6.5〜7.5,电导率10000〜20000 μ s/cm, CODcrO 〜100mg/L, Na+2000 〜4000mg/L, Cl 2500 〜5000mg/L,以 CaCO3 计总硬度 1000 〜3000mg/L。
8.如权利要求1或4所述的高温高盐废水的零排放方法,其特征在于:纳滤单元中的纳滤膜组件采用耐高温纳滤膜组件,膜材料为聚酰胺。
9.如权利要求1或4所述的高温高盐废水的零排放方法,其特征在于:纳滤单元的操作条件为:进料液侧操作压力0.3〜1.0MPa0
10.如权利要求5所述的高温高盐废水的零排放方法,其特征在于:向纳滤浓水中加入的盐类为硫酸钠或碳酸钠或两者的混合物,盐类的投加量为Ca2+:盐的摩尔比为1:1 ; 添加两者的混合物时,硫酸钠、碳酸钠的配比任意。
11.如权利要求5所述的高温高盐废水的零排放方法,其特征在于:经过钙渣沉淀后的纳滤浓水的上清液,在废水中不含COD时,直接返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理; 在废水中含有COD时,则先进入活性炭吸附单元进行活性炭吸附后再返回到纳滤单元前和纳滤进水混合进入纳滤单元循环处理。
12.如权利要求5所述的高温高盐废水的零排放方法,其特征在于:所述的活性炭为粉末活性炭或颗粒活性炭,投加量为活性炭:C0D的质量比为2:1〜10:1。
13.如权利要求4所述的高温高盐废水的零排放方法,其特征在于:所述的调酸处理所用的酸为盐酸; 调酸处理为将纳滤产水的pH调节到6.0〜6.5。
14.如权利要求1或4所述的高温高盐废水的零排放方法,其特征在于:所述膜蒸馏单元的操作条件为:进料液侧废水PH6.0〜6.5,进料液侧废水温度60°C〜80°C,进料液侧膜面流速0.6〜1.2m/s,渗透液侧真空度-0.075〜-0.095MPa。
15.如权利要求1或4所述的高温高盐废水的零排放方法,其特征在于:所述膜蒸馏单元的膜蒸馏组件的膜材料为聚偏氟乙烯、聚四氟乙烯或聚丙烯;膜孔径范围为0.15μπι〜0.2 μ m ; 所述的膜蒸馏组件形式为中空纤维式或板式; 所述的膜蒸馏组件为一组或多组串联或并联; 所述膜蒸馏单元的膜蒸馏形式为内压式真空膜蒸馏。
16.如权利要求1或4所述的高温高盐废水的零排放方法,其特征在于:所述蒸发结晶单元采用现有市售蒸发结晶器,热源采用废蒸汽加热。
17.如权利要求1或4所述的高温高盐废水的零排放方法,其特征在于:所述高温高盐废水经过纳滤单元循环处理,水回收率高于85% ; 所述高温高盐废水经过膜蒸馏单元处理,水回收率高于90%。
18.如权利要求1或4所述的高温高盐废水的零排放方法,其特征在于:处理后的高温高盐废水,产水电导率< 300μ S/cm,产水C0D„〈10mg/L,产水T0C〈3mg/L,整个系统水回收率闻于90 %。
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CN113371912A (zh) * | 2021-06-18 | 2021-09-10 | 常州大学 | 一种clt酸高盐废水中硫酸镁结晶分离工艺 |
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