本文選題：煤化工濃鹽水　切入點(diǎn)：鈍化-絡(luò)合　出處：《哈爾濱工業(yè)大學(xué)》2017年碩士論文

【摘要】：我國能源結(jié)構(gòu)的現(xiàn)狀促進(jìn)傳統(tǒng)煤化工行業(yè)向現(xiàn)代煤化工行業(yè)轉(zhuǎn)型,以煤制油、煤制天然氣等煤炭清潔利用措施來彌補(bǔ)能源結(jié)構(gòu)缺陷。但現(xiàn)代煤化工行業(yè)的高耗水、高污染現(xiàn)狀,煤炭資源、水資源的逆向分布特征以及國家環(huán)保部嚴(yán)格提出的“零排放”要求制約著煤化工行業(yè)的發(fā)展。煤化工濃鹽水作為零排放的瓶頸問題,處理難度大、成本高。以傳統(tǒng)蒸發(fā)結(jié)晶方式處理濃鹽水,產(chǎn)生結(jié)晶雜鹽的處理成本為3000元/t,其處理費(fèi)用可達(dá)到煤化工企業(yè)廢水處理總費(fèi)用的60%。為進(jìn)一步實(shí)現(xiàn)零排放要求,促進(jìn)煤化工行業(yè)穩(wěn)健發(fā)展,本課題進(jìn)行煤化工濃鹽水蒸發(fā)結(jié)晶分離工業(yè)鹽的實(shí)驗(yàn)研究,并進(jìn)行現(xiàn)場分鹽試驗(yàn)系統(tǒng)的調(diào)試與運(yùn)行,針對煤化工行業(yè)現(xiàn)有的結(jié)晶雜鹽,提出資源化利用的處理方案并進(jìn)行實(shí)驗(yàn)探究,最后分別對結(jié)晶雜鹽資源化利用工藝及蒸發(fā)結(jié)晶分鹽工藝作技術(shù)經(jīng)濟(jì)成本分析。論文根據(jù)濃鹽水水質(zhì)條件進(jìn)行鈍化-絡(luò)合預(yù)處理實(shí)驗(yàn),通過投加藥劑Ca O、MgO、PAC、PAM、Na2CO3去除濃鹽水中的硬度、堿度、活性硅及重金屬離子,經(jīng)實(shí)驗(yàn)確定藥劑最佳投加量分別為80mg/L、2500mg/L、120mg/L、2mg/L、70mg/L,對Ca2+、Mg2+、堿度、Mn2+、Al3+、總Fe及總Si的去除率分別76.07%、88.31%、44.53%、50.00%、78.64%、25.73%、49.71%,各離子去除率之和為412.99%。濃鹽水經(jīng)鈍化-絡(luò)合預(yù)處理,可減少對現(xiàn)場分鹽試驗(yàn)系統(tǒng)碟管式納濾(DTNF)單元膜污染及蒸發(fā)結(jié)晶單元腐蝕結(jié)垢問題。針對鈍化-絡(luò)合工藝對濃鹽水中重金屬離子去除效果不佳的問題,選擇煤化工濃鹽水特征重金屬離子Cu2+、總As及Ni2+,提高其在濃鹽水中的濃度進(jìn)行配水實(shí)驗(yàn),探究濃鹽水TDS、TOC及pH變化對重金屬離子去除效果的影響。實(shí)驗(yàn)確定最佳絮凝劑為FeSO4,強(qiáng)化最佳投量為90mg/L。在濃鹽水TDS 54000mg/L、TOC180mg/L,pH 6-10條件下,Cu2+、Ni2+及總As去除的最佳pH分別為9.80、9.80、7.85,去除率分別為73.00%、71.25%、46.67%。根據(jù)確定的最佳pH,在實(shí)驗(yàn)過程引入Na2CO3進(jìn)一步提高重金屬去除率,Na2CO3投量確定為120mg/L。實(shí)驗(yàn)最后引入Ca2+,分析金屬離子水合作用對重金屬離子去除的影響。根據(jù)預(yù)處理實(shí)驗(yàn)確定的投藥條件,依托煤化工濃鹽水TMC熱膜耦合分離技術(shù),進(jìn)行現(xiàn)場試驗(yàn)系統(tǒng)的調(diào)試與運(yùn)行,其工藝單元包括鈍化-絡(luò)合及樹脂軟化預(yù)處理單元、DTNF單元,多相共結(jié)晶催化氧化(HCOS)單元及蒸發(fā)結(jié)晶單元,通過DTNF單元將Cl-、SO42-分離并形成產(chǎn)水與濃水兩類水質(zhì),利用HCOS技術(shù)單元對有機(jī)物進(jìn)一步去除,TOC去除率穩(wěn)定在55.22%-61.60%,最后經(jīng)蒸發(fā)結(jié)晶單元分別結(jié)晶Na Cl、Na2SO4,其中Na Cl結(jié)晶鹽滿足精制工業(yè)鹽工業(yè)濕鹽一級指標(biāo),Na2SO4結(jié)晶鹽滿足工業(yè)鹽II類二級指標(biāo)。煤化工濃鹽水經(jīng)TMC熱膜耦合處理,總鹽理論回收率可達(dá)74.67%,其中NaCl回收率為86.42%、占總鹽49.16%,Na2SO4回收率為91.59%、占總鹽的25.51%。產(chǎn)水與濃水進(jìn)行蒸發(fā)結(jié)晶的母液理論外排比分別取1%、5%,連續(xù)外排母液0.0156m3/h,進(jìn)行結(jié)晶、生化或干化處理。論文對結(jié)晶雜鹽提出資源化利用的處理方案,即向結(jié)晶雜鹽投加濃H2SO4制備工業(yè)級NaHSO4,根據(jù)實(shí)驗(yàn)確定適宜反應(yīng)條件分別為H2SO4濃度90%-98%,投加方式1:2.5,反應(yīng)溫度130℃,反應(yīng)時間30min,蒸餾水1:1投加,采用飽和Na HSO4洗滌,所制備NaHSO4滿足工業(yè)I類一等品標(biāo)準(zhǔn)。根據(jù)該處理方案設(shè)計工藝流程,進(jìn)行經(jīng)濟(jì)成本分析,結(jié)晶雜鹽處理費(fèi)用為36.49元/t,相比其作為危廢處理,技術(shù)與經(jīng)濟(jì)性優(yōu)勢明顯。煤化工濃鹽水蒸發(fā)結(jié)晶分鹽效果良好,濃鹽水資源化利用率高,與常規(guī)蒸發(fā)結(jié)晶制備結(jié)晶雜鹽及自然蒸發(fā)工藝相比,濃鹽水處理費(fèi)用分別為50.32元/t、234.34元/t、204.35元/t,固(危)廢處理費(fèi)用占比分別為16.67%、84.39%、96.78%,蒸發(fā)結(jié)晶分鹽工藝處理費(fèi)用低,產(chǎn)生固(危)廢量少,資源化利用率高,具有明顯技術(shù)與經(jīng)濟(jì)優(yōu)勢。本研究以煤化工濃鹽水蒸發(fā)結(jié)晶分鹽及資源化利用為核心,進(jìn)行濃鹽水的預(yù)處理實(shí)驗(yàn)及現(xiàn)場分鹽試驗(yàn)系統(tǒng)運(yùn)行與調(diào)試,提出結(jié)晶雜鹽資源化利用方案,并對結(jié)晶雜鹽資源化利用及煤化工濃鹽水蒸發(fā)結(jié)晶分鹽工藝作經(jīng)濟(jì)性分析。結(jié)晶雜鹽資源化利用處理成本低,可從根本上解決結(jié)晶雜鹽產(chǎn)量大、處理成本高、易二次污染的問題。煤化工濃鹽水TMC熱膜耦合工業(yè)鹽分離技術(shù)總鹽回收率高、結(jié)晶鹽純度高、母液排量小、產(chǎn)生危廢少、清潔水回收率高,具有良好的工程應(yīng)用前景。
[Abstract]:Status quo of China's energy structure and promote the transformation of traditional coal chemical industry to a modern coal chemical industry, the coal oil, coal and natural gas and other clean coal utilization measures to make up for the defects of the energy structure. But the high water consumption of modern coal chemical industry, high pollution, coal resources, water resources distribution and reverse state environmental protection the Ministry strictly proposed "zero emissions" requirement restricts the coal chemical industry. The development of coal chemical industry as the bottleneck problem of brine zero emissions, processing difficulty, high cost. Concentrated saline processing in the traditional way of evaporation and crystallization of crystal salt, produce treatment cost is 3000 yuan /t, the treatment cost can be achieved in coal chemical industry the total cost of the wastewater treatment 60%. for the further implementation of zero emission requirements, and promote the healthy development of coal chemical industry, this paper studied the coal chemical separation of industrial salt brine evaporation and crystallization, and in the field Commissioning and operation of salt test system, the coal chemical industry the existing crystal salt, put forward a plan to deal with resource utilization and experimental research, finally the crystal salt resource utilization technology and process technology of evaporation and crystallization of salt. The paper analyzed the cost according to the water quality conditions of brine experiments passivated complexation pretreatment by adding medicament to Ca O, MgO, PAC, PAM, Na2CO3 removal of brine in alkalinity, hardness, silicon and heavy metal ion activity, through experiments to determine the optimum dosage of drugs were 80mg/L, 2500mg/L, 120mg/L, 2mg/L, 70mg/L, Ca2+, Mg2+, Mn2+, Al3+, total alkalinity. Fe and the total removal rate of Si were 76.07%, 88.31%, 44.53%, 50%, 78.64%, 25.73%, 49.71%, the removal rate of 412.99%. ion and brine after passivation complexation pretreatment can reduce the salt field test system of disc tube nanofiltration (DTNF) membrane fouling and unit The evaporation crystallization unit corrosion and scaling problem. Aiming at the problem of poor removal of heavy metal ions in the brine passivation complexation process, selection of coal chemical brine characteristics of heavy metal ion Cu2+, total As and Ni2+, increasing its concentration in the brine in the water experiment, inquiry concentrated salt water TDS, the removal effect of heavy metals ion TOC and pH changes. The optimal flocculant was FeSO4, the best strengthening dosage of 90mg/L. in brine and TDS 54000mg/L, TOC180mg/L, pH 6-10, Cu2+, pH Ni2+ and the best As removal was 9.80,9.80,7.85, the removal rates were 73%, 71.25%, 46.67%. pH is determined according to the best, the introduction of Na2CO3 in the experimental process to further improve the removal rate of heavy metal, the dosage of Na2CO3 was 120mg/L. into Ca2+ at the end of the experiment, effect of metal ion hydration on the removal of heavy metal ions. According to the pretreatment experiment The dosing condition, relying on coal chemical brine TMC thermal coupling membrane separation technology, debugging and running test system, the process unit includes a passivation and chelate resin softening pretreatment unit, DTNF unit, multi phase catalytic oxidation of CO crystallization (HCOS) unit and evaporation crystallization unit, the DTNF unit Cl- SO42-, separation and the formation of water and concentrated water two water quality, further removal of organic matter by using the technology of HCOS unit, the removal rate of TOC was stable in 55.22%-61.60%, the evaporation crystallization unit respectively Cl Na2SO4, Na crystal, Na Cl crystal salt refining industrial salt industry meet the wet salt level index, Na2SO4 crystal salt meet industrial salt II class of two grade indicators. The coal chemical brine by TMC thermal coupling membrane treatment, the total salt theoretical recovery rate reaches 74.67%, the recovery rate of NaCl was 86.42%, accounting for 49.16% of total salt, Na2SO4 recovery rate was 91.59%, accounting for 25.51%. of total salt and water production The theory of mother liquor evaporation concentrated water and parallelism were taken 1%, 5%, continuous discharge liquor 0.0156m3/h, crystallization, biochemical or dry processing. The crystal salt solution is presented to resource utilization, namely to crystal salt equipment industrial grade NaHSO4 and concentrated H2SO4 system, according to the experiment to determine the appropriate the reaction conditions were H2SO4 concentration 90%-98%, 1:2.5 dosage, reaction temperature 130 C, reaction time 30min, 1:1 dosage of distilled water, washing with saturated Na HSO4, prepared by NaHSO4 I meet the industrial grade a standard. According to the scheme design process, economic cost analysis, the cost for handling crystal salt 36.49 yuan /t, compared to the hazardous waste treatment, technical and economic advantages. Coal chemical Brine Evaporation and crystallization of salt well, brine resource utilization rate is high, and the conventional evaporation crystallization preparation of crystal salt and natural evaporation. Art than brine treatment costs were 50.32 yuan /t, 234.34 yuan /t, 204.35 yuan /t, solid waste treatment costs (risk) accounted for 16.67%, 84.39%, 96.78%, evaporation and crystallization of salt treatment process of low cost, produce less waste solid (hazardous), resource utilization rate is high, has the obvious technical and economic advantages. The research on the coal chemical Brine Evaporation and crystallization of salt and resource utilization as the core of the brine pretreatment experiment and field operation and debugging experiment of salt system, put forward the crystallization solutions using mixed salt resources, and the crystal salt resource utilization and coal chemical brine evaporation crystallization salt technology economic analysis. Crystal salt resource utilization of low processing cost, can fundamentally solve the crystal salt yield, high processing cost, easy two pollution problems. The coal chemical brine TMC thermal coupling membrane separation technique of industrial salt salt high recovery rate, crystallization The purity of salt is high, the discharge of mother liquid is small, the waste is less, the recovery rate of clean water is high, and it has a good prospect of engineering application.

【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：X784;TQ028.6

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 周海;;振動膜技術(shù)在高含鹽廢水處理中的應(yīng)用[J];中國給水排水;2017年02期

2 王彥飛;楊靜;王婧瑩;李亞楠;胡佳琪;沙作良;;煤化工高濃鹽廢水蒸發(fā)處理工藝進(jìn)展[J];無機(jī)鹽工業(yè);2017年01期

3 肖揚(yáng);;環(huán)保部設(shè)立煤化工項目環(huán)境準(zhǔn)入七道門檻[J];上�；�;2016年12期

4 崔粲粲;梁睿;羅，

本文編號：1660441