CN107265731A - 一种含有酚钠盐废水的回收处理方法 - Google Patents
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- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002351 wastewater Substances 0.000 title claims abstract description 27
- 238000011084 recovery Methods 0.000 title claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 26
- 238000001728 nano-filtration Methods 0.000 claims abstract description 24
- 230000007935 neutral effect Effects 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 239000012074 organic phase Substances 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims abstract description 3
- 238000013517 stratification Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000010025 steaming Methods 0.000 abstract description 11
- 239000008346 aqueous phase Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 238000000071 blow moulding Methods 0.000 abstract description 4
- 150000002989 phenols Chemical class 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 9
- 239000003245 coal Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 206010019233 Headaches Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 phenols sodium salt Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/066—Overpressure, high pressure
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
本发明公开了一种含油酚钠盐废水的回收处理方法,将原料罐中含油酚钠盐废水经过加压后,通过陶瓷纳滤膜组件过滤分离得到富含酚钠盐的分离相和富含中性油废水相,所述富含酚钠盐的分离相经过酸解后静置分层得到上层含酚的有机相回收产品;所述中性油水相回流至原料罐中并循环送至陶瓷纳滤膜组件进行过滤分离,经过陶瓷纳滤膜组件连续过滤分离提升中性油含量后,经过蒸馏或精馏处理得到中性油副产品。本发明能代替传统工艺中的蒸吹工艺,节约了能源消耗,同时减少后续工艺中的酸碱用量,提高粗酚品质,降低该工艺的环境污染及其处理难度。
Description
技术领域
本发明属于能源化工技术领域,尤其涉及煤化工产生的含酚钠盐废水的回收处理技术。
背景技术
我国的能源资源主要以煤炭和石油、天然气为主,其中煤炭资源相对丰富,也是许多重要化工品的主要原料。随着社会发展今年来中国对能源和化工品的需求呈现较高的增长速度,比如通过煤化工制备甲醇、二甲醚、烯烃、煤制油等产品。但随着煤化工产品需求的日益增长,煤化工的三废处理成为环境污染的头疼问题。煤化工产业,特别是焦化厂产生的废气都会含有酚和中性油,传统的废气处理方式主要是采用蒸汽吹蒸工艺,该工艺不仅要消耗大量蒸汽,其除油效果不佳,至使下游酸分解工艺中需要额外加入大量的酸,对酚钠盐进行处理,同时增加了相关产业废水的处理难度。
如图1所示的传统蒸汽吹蒸工艺:粗酚钠盐废水经换热器预热后从上部进入蒸吹柱,与来自底部的蒸汽在蒸吹柱中进行脱油,从蒸吹柱顶部的蒸汽经换热器换热后回到分相槽中,进行油水分离,水相进污水处理系统。该工艺对酚钠盐中的中性油等杂物去除率仅能到0.05%。蒸吹柱及换热器堵塞严重,蒸吹效果下降,净酚盐纯度不高,中性油含量高达0.8%--1%,后续工艺中需要酸浓度(氧化中性油)及酸量增大,同时导致后续设备腐蚀、用碱量也增大,极大的影响正常生产运行。
发明内容
发明目的:针对上述现有存在的问题和不足,本发明的目的是提供一种含有酚钠盐废水的回收处理方法,能代替传统工艺中的蒸吹工艺,节约了能源消耗,同时减少后续工艺中的酸碱用量,提高粗酚品质,降低该工艺的环境污染及其处理难度。
技术方案:为了解决上述技术问题,本发明采用以下技术方案:一种含油酚钠盐废水的回收处理方法,将原料罐中含油酚钠盐废水经过加压后,通过陶瓷纳滤膜组件过滤分离得到富含酚钠盐的分离相和富含中性油废水相,所述富含酚钠盐的分离相经过酸解后静置分层得到上层含酚的有机相回收产品;所述中性油水相回流至原料罐中并循环送至陶瓷纳滤膜组件进行过滤分离,经过陶瓷纳滤膜组件连续过滤分离提升中性油含量后,经过蒸馏或精馏处理得到中性油副产品。
作为优选方案,所述陶瓷纳滤组件为孔径为5~20nm的陶瓷纳滤膜,所述陶瓷纳滤膜的采用氧化锆涂层。
作为优选方案,所述含油酚钠盐废水进入陶瓷纳滤膜组件的压力为7~20bar。
作为优选方案,所述富含酚钠盐的分离相经过硫酸分解。
有益效果:与现有技术相比,本发明。
附图说明
图1为含油酚钠盐废水传统处理工艺示意图;
图2为本发明所述含油酚钠盐废水的处理流程示意图。
其中,原料罐1、陶瓷纳滤膜组件2、萃取分离塔3、精馏塔4。
具体实施方式
下面结合附图和具体实施例,进一步阐明本发明,应理解这些实施例仅用于说明本发明而不用于限制本发明的范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。
如图1所示,本发明的含油酚钠盐废水的回收处理方法,焦化厂产生的含酚废气经过碱液吸收后形成含油酚钠盐废水,并储存在原料罐中。将原料罐中含油酚钠盐废水经过加压至7~20bar,然后送至陶瓷纳滤膜组件过滤分离得到富含酚钠盐的分离相和富含中性油废水相,其中洗脱用水来自后端萃取分离的水相。其中,富含酚钠盐的分离相送至萃取分离塔中,在硫酸作用下分解并经过静置分层,得到上层含酚的有机相,作为酚回收产品;而下层的硫酸钠水相作为废水处理。所述中性油水相回流至原料罐中并循环送至陶瓷纳滤膜组件进行过滤分离,经过陶瓷纳滤膜组件连续过滤分离提升中性油含量后,经过蒸馏或精馏处理得到中性油副产品。该过程中,中性油等物质在原料罐中富集到一定浓度,由供料泵排出至分相罐进行中性油回收。
本发明采用5nm~20nm之间的陶瓷纳滤膜组件,可稳定控制净酚盐中油含量≤15mg/L,可代替蒸吹工艺,节约能源,同时减少后期酸(务须硫酸的氧化性)、碱用量及设备的腐蚀。纳米陶瓷膜采用氧化锆涂层,其过滤孔径可控制到1nm,5nm,20nm等多种规格。本发明介于超滤和反渗透之间的压力驱动膜分离过程。核心原件-纳滤膜材料由于具有纳米尺寸的微孔(孔径:1~2nm)且表面荷电,使得纳滤膜不仅可以截留分子量在200~1000Da的有机小分子,而且对离子具有一定的截留效应。
主要通过纳米陶瓷膜工艺将酚钠盐中的酚钠盐水溶液从高含油的酚钠盐废水中提取出来,同时油相在原料罐中不断富集,一定浓度后进入分相罐中进行分相回收中性油。本工艺可以替代后续蒸吹工艺,降低工艺运行成本,同时提高粗酚品质,使得资源有效回收。本技术方案主要由纳滤陶瓷膜、陶瓷膜膜壳、供料泵、阀门等其他组件构成。陶瓷膜与膜壳之间通过特殊材质的密封构件进行密封,保证料液不发生串料现象。运行过程中,废水中的中性油等物质无法通过纳米级滤芯,被保留在滤芯的内侧,回流至原料罐,酚类及水相由滤芯侧面排出至接收罐,原料罐中加入洗脱水将料罐中的酚从中洗脱出。
Claims (4)
1.一种含油酚钠盐废水的回收处理方法,其特征在于:将原料罐中含油酚钠盐废水经过加压后,通过陶瓷纳滤膜组件过滤分离得到富含酚钠盐的分离相和富含中性油废水相,所述富含酚钠盐的分离相经过酸解后静置分层得到上层含酚的有机相回收产品;所述中性油水相回流至原料罐中并循环送至陶瓷纳滤膜组件进行过滤分离,经过陶瓷纳滤膜组件连续过滤分离提升中性油含量后,经过蒸馏或精馏处理得到中性油副产品。
2.根据权利要求1所述含油酚钠盐废水的回收处理方法,其特征在于:所述陶瓷纳滤组件为孔径为5~20nm的陶瓷纳滤膜,所述陶瓷纳滤膜的采用氧化锆涂层。
3.根据权利要求1所述含油酚钠盐废水的回收处理方法,其特征在于:所述含油酚钠盐废水进入陶瓷纳滤膜组件的压力为7~20bar。
4.根据权利要求1所述含油酚钠盐废水的回收处理方法,其特征在于:所述富含酚钠盐的分离相经过硫酸分解。
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CN109336727A (zh) * | 2018-09-21 | 2019-02-15 | 蔚永岗 | 一种粗酚中中性油的提取技术 |
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CN109336727A (zh) * | 2018-09-21 | 2019-02-15 | 蔚永岗 | 一种粗酚中中性油的提取技术 |
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