CN105600914B - 一种有机废液及污泥的间接换热型超临界水氧化系统 - Google Patents
一种有机废液及污泥的间接换热型超临界水氧化系统 Download PDFInfo
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- 238000010525 oxidative degradation reactions Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound 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[P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000008247 solid mixtures Substances 0.000 description 1
- 239000002904 solvents Substances 0.000 description 1
- 239000000126 substances Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound 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[S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
-
- 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
Abstract
本发明公开了一种有机废液及污泥的间接换热型超临界水氧化系统，通过设置回热器、预热器，借助中间介质循环，实现间接地将超临界水氧化反应出水的热量传递给后续待处理物料。相对于反应出水直接对待处理物料进行预热的换热设备，该工艺中的预热器/回热器仅其内管需采用高端耐蚀合金、外管采用碳钢或者低合金钢即可，从而大大降低了超临界水氧化工艺中预热‑冷却设备的投资成本。此外，预热器/回热器外管侧为干净的除盐水，避免了换热器外管侧走脏流体的堵塞风险。此外，工艺末端设置的三相分离子系统可实现超临界水氧化反应出水中液、固、气三相的自动连续在线分离。该工艺可广泛应用于各类有机废液及污泥的超临界水氧化处理领域。
Description
一种有机废液及污泥的间接换热型超临界水氧化系统 【技术领域】
[0001] 本发明属于超临界水处理有机废物领域，具体涉及一种有机废液及污泥的间接换 热型超临界水氧化系统。 【背景技术】
[0002] 超临界水(Supercritical Water，简称SCW)是指温度和压力均高于其临界点（Tc = 374.15°C，Pc = 22.12MPa)的特殊状态的水。超临界水氧化（Supercritical Water 〇xidation，SCW0)是利用超临界水独特的理化性质来实现有毒有害有机污染物的高效氧化 降解。与普通的液态水相比，超临界水的各种理化性质发生了显著的变化:密度、黏度、离子 积均明显下降，扩散系数较高;水分子间的氢键减弱;介电常数变得极小，25MPa下由室温下 的80左右下降至温度大于或者等于40(TC时的小于2,该值大致相当于标准状态下一般有机 溶剂的介电常数。因此，在超临界水体系中，氧气、空气、过氧化氢、水及绝大多数有机物可 以任意比例互溶，气液相界面消失，超临界水氧化体系成为均相反应体系，消除了相间的传 质传热阻力，从而加快了反应速度，可在几秒至几分钟内将有机物彻底氧化降解为⑶2、 H20、N2及其他一些有机小分子化合物，对大多数有机废物的去除率高达99.9%。此外，无机 盐类在SCW中的溶解度极低，容易被分离出来，处理后的液体为洁净的水；当有机废水中有 机物质量浓度超过2%时，可以依靠反应放热维持系统热量平衡，无需外界补充热量;设备 体积小、安全性好、符合封闭性要求。超临界水氧化技术在处理难降解、有毒有害有机物方 面表现出了极大的技术优势。
[0003] 超临界水氧化反应为高温高压反应，因而待处理物料的预热、反应出水的降温是 超临界水氧化工艺中必不可少的环节。对于传统超临界水氧化工艺，通常借助换热器，待处 理物料作为冷却介质对超临界水氧化反应出水进行降温，同时实现待处理物料的预热升 温。预热升温后的待处理物料接着进入反应器，实现超临界水氧化系统的连续运行。由于 320〜410°C范围的临界点附近高密度水区，水的介电常数和无机盐的溶解度都很大，该温 度段为腐蚀敏感区，为传统超临界水氧化工艺中，设备腐蚀最严重的工艺段，而该工艺段恰 恰对应于上述换热器的冷、热流体侧，对该换热器的持久可靠运行构成了潜在威胁。
[0004] 此外，各类有机废液及污泥等待处理物料中往往含有大量的强腐蚀性组分如氯根 等，当待处理物料内有机污染物中还含有卤素、硫或者磷等杂原子，在超临界水氧化反应过 程还会产生相应的无机酸。此外，为了保证有机污染物的氧化降解效果，氧化剂的供给往往 是过量的，有时氧化系数(氧化剂的供给量与有机废物氧化对氧化剂的消耗量的比值)甚至 可高达3以上，超临界水氧化反应出水中往往含有较高含量的残留氧化剂。因此，超临界水 氧化反应出水的腐蚀性常常更强于待处理物料。对于上述换热器，其冷却介质为待处理物 料，热流体为超临界水氧化反应出水。若采用耐压能力强的套管式换热器时，则内管的内外 壁面、外管的内壁面皆面临着严重的腐蚀威胁。换热设备的内外管皆须采用高端耐蚀合金， 其制造成本较高。此外相对于内管流程，外管流程的局部堵塞可能性较大，当外管流程中流 体为无机盐或者不溶性固体含量较高的超临界水流体时，极易导致外管流程的堵塞事故。
[0005]因此，针对各类有机废液及污泥超临界水氧化工艺的开发，需要降低预热-冷却阶 段设备投资及其运行风险，以确保超临界水氧化装置的低投资和持久运行可靠性。
[0006] 城市污泥和各类工业污泥产量巨大，其为超临界水氧化工艺的重点处理对象之 一，因此超临界水氧化系统的待处理物料中往往含有一定量的不溶性固体，因此避免不溶 性固体在超临界水氧化装置内的沉积堵塞、实现超临界水氧化反应出水的连续在线三相 (液相、气相产物、不溶性固体)分离，对于提高超临界水氧化工艺的市场竞争力同样具有重 要意义。 【发明内容】
[0007] 本发明的目的是针对背景技术中待处理物料与反应出水直接换热设备的投资高、 腐蚀/±^塞风险大的问题，以及避免装置中不溶性固体沉积堵塞与实现反应出水连续稳定 三相分离的紧迫性，提供一种有机废液及污泥的间接换热型超临界水氧化系统。< U [0008]为达到上述目的，本发明采用以下技术方案予以实现：
[0009] 一种有机废液及污泥的间接换热型超临界水氧化系统，包括超临界水氧化反应物 系统、物料预处理系统、氧气供应系统以及中间介质导热系统;反应物料由物料预处理系统 进入超临界水氧化反应物系统，中间介质导热系统进行热交换;超临界水氧化反应物系统 包括反应器以及设置于末端的三相分离子系统，反应完的物料经三相分离子系统外排.氧 气供应系统用于向反应器中提供氧气。 ’
[0010]本发明进一步的改进在于：
[0011]所述物料预处理系统包括物料缓冲罐，物料缓冲罐的出口与超临界水氧化反应物 系统的入口相连通;物料缓冲罐的入口分别连接不溶物过滤器和储药箱;不溶物过滤器的 入口连接物料输入管道，出口与物料缓冲罐之间的管路上设置研磨泵;储药箱与物料缓冲 罐之间的管路上设置加药泵。
[0012]所述氧气供应系统包括液氧罐，液氧罐的出口依次连接液氧泵、液氧气化器、氧气 缓冲罐以及氧气调压器，氧气调压器的出口与反应器的入口相连通。
[0013]所述超临界水氧化反应物系统包括物料泵，物料栗的入口与物料预处理系统的出 口相连通，物料泵的出口连接预热器内管，预热器的内管出口与反应器的入口相连通，反应 器的出口^接回热器内管，回热器的内管出口通过降压器与三相分离子系统的入口相连 通，三相分离子系统的出口与系统出水外排管道相连通。
[00M]所述中间介质导热系统包括管道增压栗，管道增压泵的入口与预热器的外管出口 相连，出口与回热器的外管入口相连；回热器的外管出口通过加热器与预热'器的外管入口 相连通。
[0015]所述管道增压泵与预热器之间的管道上还设置有调压器。
[0016]还包括fe盐水相，除盐水箱的出口分为两路，一路连接至预热器与管道增压栗之 间的管道上，另一路连接至物料泵的入口处。 _7]所述降压器出口依次连接气液分离器和在线微过滤器，在线微过滤 统出水外排管道相连通。
[0018]所述降压器出口依次连接在线微过滤器和气液分离器，气液分离器的出口与系统 出水外排管道相连通；
[0019]所述降压器的出口连接三相分离器，三相分离器的液体出口与系统出水外排管道 相连通。
[0020]与现有技术相比，本发明具有以下有益效果：
[0021]本发明通过设置中间介质导热系统，实现间接地将超临界水氧化反应出水的热量 传递给后续待处理物料。相对于反应出水直接对待处理物料进行预热的换热设备，本发明 预热器和回热器仅其内官需米用尚端耐蚀合金、外管采用碳钢或者低合金钢即可，从而大 大降低了超临界水氧化工艺中预热-冷却设备的投资成本。
[0022] 进一步的，本发明不溶物过滤器和研磨泵，可以将超临界水氧化装置进口物料中 不溶性固体颗粒的粒径控制到50微米以下，较小的不溶性固体颗粒尺寸，大大减小了其在 超临界水氧化装置内沉积，堵塞设备的可能性，提高了装置的运行可靠性。
[0023] 进一步的，本发明预热器和回热器的内管侧走腐蚀性流体(预热器内管为待处理 物料、回热器内^为超临界水氧化反应出水），外管侧为干净的除盐水，因此预热器与回热 器仅其内管需采用高端耐蚀合金、外管采用碳钢或者低合金钢即可，从而大大降低了超临 界水氧化工艺中预热-冷却设备的投资成本。此外，外管侧为干净的除盐水，避免了外管侧 走脏流体(待处理物料或者反应出水)的堵塞风险。
[0024]进一步的，本发明三相分离子系统可实现超临界水氧化反应出水中液相、不溶性 固相微颗粒以及气相产物等液、固、气三相的连续自动在线分离。 【附图说明】
[0025]图1为本发明的整体结构示意图。
[0026]其中，丨-不溶物过滤器;2—研磨栗；3—物料缓冲罐;4_物料泵；5_预热器;6_除盐水 ^、; 7-反应器;8-回热器;9-降压器；10-气液分离器；U—在线微过滤器；12_三相分离器；13一 管道增压泵；14-加热器;I5-液氧罐；16_液氧栗；17_液氧气化器；18_氧气缓冲罐;19_氧气 调压器;20-储药箱;21-加药泵;22_调压器;101—开关阀；1〇2_开关阀；1〇3_开关阀。 【具体实施方式】
[0027]下面结合附图对本发明做进一步详细描述：
[0028]参见图丨，本发明包括物料预处理系统、中间介质导热系统、氧气供应系统、超临界 水氧化反应物系统。其中：
[0029]物料预处理系统包括不溶物过滤器1、研磨泵2、物料缓冲罐3、储药箱20以及加药 ^21，研磨栗2可以研磨不溶性固体粒径至50微米以下。不溶物过滤器丨入口连接物料输入 管道，不溶物过滤器1出口连接研磨栗2入口，研磨泵2出口连接物料缓冲罐3入口，储药箱2〇 的出口连接加药泵21，加药栗21的出口连接物料缓冲罐3入口。
[0030]中间介质导热系统包括预热器5、管道增压栗13、回热器8以及加热器14,预热器5 夕卜管入□连接加热器14出□，预热器5外管出□连接管道增压泵13，管道增压泵13出口接至 回热器8外管，回热器8外管出口连接加热器14入口。
[0031]、氧气供应系统包括液氧罐15、液氧杲ie、液氧气化器17、氧气缓冲罐18以及氧气调 压器19。液氧罐15连接液氧栗16，液氧栗I6接至液氧气化器丨7，液氧气化器17出口连接氧气 缓冲罐18,氧气缓冲罐18出口连接氧气调压器19，氧气调压器19出口接至反应器7入口。 ^ u〜姐七汉脞物糸统包括物料泵么预热器&反应器夂回热器心降压器9以及 二相分禺^系统，物料泵4入口连接物料缓冲罐3出口，物料泵4出口接至预热器5内管入口， ^热器5内管出□鞋反应器7人□，反应器了出口接至回減纳管，随器S内管出口雜 P牛压器9，f讎9^ □接至三相分离子絲、三齡舒系纟础a鞋絲出水外排管道。 [0033]、二^分离子魏健气液分离器1Q、在线微过滤器11或者气麵三相分离器I2， 所述气液触器1G连撕压器9出|=|、气液分离獅出口鞋在纖过麵u、在线微过滤 器11出口连接系统出水外排管it;或者在线微过滤器【【入口连撕压器g出口、在线微过滤 ^11出[^连接气液分离器10入口、气液分离器10出口连接系统出水外排管道;或者气液固 三相分离器12入口连接降压器9出口，气液固三相分离器12出口接至系统出水外排管道。 [0034]本发明的原理及过程：
[0035]系统启动前期，首先由工艺界外向除盐水箱6补充除盐水。来自除盐水箱6的除盐 水一支路，经开关阀103至管道增压泵I3。管道增压泵位于中间介质回路的最低点，在管道 增压栗j3的泵送作用下，中间介质依次流经回热器8外管、加热器14、预热器5外管、调压器 22,进行中间介质回路的充水;充水完成后通过调小位于中间介质回路最高点的调压器22 的开度，实现中间介质回路的升压，充水升压完成后关闭开关阀丨03。同时，来自除盐水箱6 的另一支路，经开关阀102至物料栗4。在物料泵4的栗送作用下除盐水依次流经预热器5内 反应器7、回热器8内管、降压器9、三相分离子系统，最终进入系统出水外排管道。逐步调 节降压器9,使反应器7处压力逐渐升高至超临界压力。启动加热器14对中间介质进行补热， 管道增压泵13作为中间介质循环动力，经过一定时间的循环加热，可使得反应器入口温度 升高至目标值，即完成了系统的升温。
[0036]系统升压升温完成后，物料泵4进口物料由来自除盐水箱6的除盐水切换为来自物 料缓冲罐3的待处理物料。经过不溶物过滤器丨的过滤、研磨泵2的研磨处理，物料缓冲罐3中 不溶性固体颗粒的粒径可控制在50微米以下;此外，来自储药箱20的药剂，经加药泵21进入 物料缓冲罐3，在物料缓冲罐内搅拌器作用下，可实现物料特性的均质调配，满足超临界水 氧化装置对系统进料的要求。调配好的待处理物料经物料泵4流入预热器5内管中被预热器 5外管中高温中间介质预热至目标预热温度，继而进入反应器7;来自液氧罐15的液氧依次 流经液氧泵16、液氧气化器17,继而以氧气形式进入氧气缓冲罐18,经氧气调压器19调压后 进入反应器7。在反应器7内，达到预热温度的待处理物料与氧气相遇发生氧化反应，放出一 定的热量。超临界水氧化反应出水进入回热器8内管将热量传递给回热器8外管的中间介 质。在管道增压荥13的作用下，中间介质在中间介质回路内循环流动，于回热器8外管吸收 内管反应出水的热量，经加热器14必要时需适当补热，流入预热器5外管将热量传递给预热 器5内管中物料，实现待处理物料的预热。来自回热器8内管的已冷却反应出水经降压器9降 至适当压力后，进入三相分离器子系统，实现反应出水的三相分离。
[0037]三相分离子系统的实施流程可分为三种，见图1。其一，先分离气相，再实现液固分 离:来自降压器9的低温反应出水，首先进入气液分离器1〇,气相产物及残留氧气等从其顶 部排出，液固混合物由其底部出口进入在线微过滤器11;在线微过滤器11内实现液固分离， 固相残渣由其排污口连续或者间歇排出，液相由其排液口流出，继而进入系统出水外排管 道。其二，先脱出固相残渣，后实现气液分离:来自降压器9的低温反应出水，首先进入在线 微过滤器11，固相残渣由其底部排污口连续或者间歇排出；气液混合物进入气液分离器10， 气+0广物及残^气等从其顶部排出，液相由其排液口流出，继而进入系统出水外排管道。 其三，同时实现三相分离:来自降压器9的低温反应出水进入气液固三相分离器12,相产物 及残留氧气等从其顶部排出，固相残渣由其底部排污口连续或者间歇排出，液相由其排液 口流出，继而进入系统出水外排管道。
[0038]以上内容仅为说明本发明的技术思想，不能以此限定本发明的保护范围，凡是按 照本发明提出的技术思想，在技术方案基础上所做的任何改动，均落入本发明权利要求书 的保护范围之内。
Claims (7)
1. -种有机废液及污泥_接__临界水氧化雜，其特征在于，包 氧化反应物系统、物料预处理系统、氧气供应系统以及中间介质导热系统;反应物料 预处理系统进人雜界水輸反应物通，中间介质导魅纟纖㈣交换;雜界n 反应物系统包括反应器⑺以及设置于末端的三相分离子^统，反应完的物料经二相分窗 子系统外排;氧气供应系统用于向反应器⑺中提供氧气； < 所述超临界水氧化反应物系统包括物料泵(4)，物料杲(4)的入口与物料预处理系统 出口相连通，物料泵⑷的出口连接预热器⑸内管，预热器⑸的内管出口与反应器⑺的 入^相连通，反应器⑺的出口连接回热器⑻内管，回热器⑻的内管出口通过降压器(9) 与三相分离子系统的入口相连通，三相分离子系统的出口与系统出水外排管道相连通； 所述中间介质导热系统包括管道増压栗Q3)，管道增压泵（1；3)的入口与预热器(5)的 外管出口相连，出口与回热器⑻的外管入口相连；回热器⑻的外管出口通过加热器（14) 与预热器⑸的外管入口相连通； 所述物料预处理系统包括物料缓冲罐(3)，物料缓冲罐(3)的出口与超临界水氧化反应 物系统的入口相连通;物料缓冲罐(3)的入口分别连接不溶物过滤器（1)和储药箱(2〇);不 溶物过滤器(1)的入口连接物料输入管道，出口与物料缓冲罐(3)之间的管路上设置研磨泵 (2);储药箱(20)与物料缓冲罐(3)之间的管路上设置加药泵(21);研磨泵⑵研磨出的不溶 性固体粒径<50um。
2. 根据权利要求1所述的有机废液及污泥的间接换热型超临界水氧化系统，其特征在 于，所述氧气供应系统包括液氧罐(15)，液氧罐(15)的出口依次连接液氧泵(I6)、液氧气化 器（I7)、氧气缓冲罐（18)以及氧气调压器（19)，氧气调压器（19)的出口与反应器⑺的入口 相连通。
3. 根据权利要求1所述的有机废液及污泥的间接换热型超临界水氧化系统，其特征在 于，所述管道增压泵(1¾与预热器(5)之间的管道上还设置有调压器(22)。
4. 根据权利要求3所述的有机废液及污泥的间接换热型超临界水氧化系统，其特征在 于，还包括除盐水箱(6)，除盐水箱(6)的出口分为两路，一路连接至预热器⑸与管道增压 泵(13)之间的管道上，另一路连接至物料泵⑷的入口处。
5. 根据权利要求1所述的有机废液及污泥的间接换热型超临界水氧化系统，其特征在 于，所述降压器⑼出口依次连接气液分离器(10)和在线微过滤器(11)，在线微过滤器(11) 的出口与系统出水外排管道相连通。
6.根据权利要求1所述的有机废液及污泥的间接换热型超临界水氧化系统^其特征在 于，所述降压器(9)出口依次连接在线微过滤器（11)和气液分离器（10)，气液分离器（1〇)的 出口与系统出水外排管道相连通。 /
7.根据权利要求1所述的有机废液及污泥的间接换热型超临界水氧化系统，其特征在 于，所述降压器(9)的出口连接三相分离器（12)，三相分离器（1¾的液体出口与系统出水外 排管道相连通。
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