石油天然氣脫硫劑的研究

2003年11月精細石油化SPECIALITY PETROCHEMICALS石油天然氣脫硫劑的研究閆仁庚奚惠民楊濤張旭龍王吉德(1.新疆大學(xué)化學(xué)化工學(xué)院,烏魯木齊830046;2.伊犁師范學(xué)院化學(xué)系,伊犁835000;3.克拉瑪依采油二廠(chǎng)2號氣站,克拉瑪依834000;4.克拉瑪依金葉公司,克拉瑪依834000摘要:以活性炭為原料,乙醇胺為添加劑,碳酸鈉為改性劑制成脫硫劑,考察了活性炭及添加劑的種類(lèi)、改性劑及添加劑的含量以及不同制備條件對活性炭脫硫活性能的影響。結果表明最優(yōu)活性炭脫硫劑組成是:將煤質(zhì)活性炭放在5%的碳酸鈉溶液里浸漬改性,添加0.1%的乙醇胺。產(chǎn)物經(jīng)中試和現場(chǎng)專(zhuān)家鑒定,其脫硫性能優(yōu)于市售同類(lèi)產(chǎn)品關(guān)鍵詞:活性炭脫硫劑吸附硫化氫天然氣是一種廉價(jià)高效的燃料,已被廣泛使丙醇胺等均為分析純試劑。用。新疆油田公司的彩南油田2*氣站和石西油721分光光度度計。田的天然氣中含硫量均超過(guò)國家標準規定的201.2脫硫劑的制備mg/m3,氣站現用的市售脫硫劑價(jià)格及運輸成取一定量的煤制炭用蒸餾水煮沸,洗凈后,在本較高,為此筆者開(kāi)發(fā)了一種新脫硫劑。l10℃烘4h,然后用一定濃度的碳酸鈉溶液及活性炭應用于氣體脫硫最初是利用其選擇物0.01%~1.0%的添加劑溶液浸漬12h,潷干,于理吸附作用,而目前用浸漬過(guò)的活性炭脫硫的研110℃烘干12h,直至干燥究較多,主要集中在脫硫機理及添加活性組分的1.3脫硫劑的實(shí)驗室評價(jià)裝置研究上。在活性炭中添加適當的改性劑可以顯著(zhù)硫化氫入口本底取樣門(mén)增強活性炭的吸附性能,從而既可降低活化能,又可以提高硫容2。轉子流量讠l實(shí)驗吸收瓶吸附器1.1主要試劑與儀器脫硫劑B:2108干脫硫劑;煤制炭,新疆昌吉圖1脫硫劑的實(shí)驗室評價(jià)裝置萬(wàn)名活性炭廠(chǎng);對氨基二甲苯胺鹽酸鹽,CR;收稿日期:2002-10-22;修改稿收到日期:2003-08-13作者簡(jiǎn)介:胡云霞(1972-),女,助教,主要進(jìn)行油田化學(xué)品Na2CO3、鄰苯三酚、乙二胺、苦味酸、乙醇胺、二異的研究工作,E-mail:awangid@xju.edu.cnSTUDY ON SYNTHESIS OF GLYCEROL TRIOLEATEZhang Yuecheng, Hu Qiuyi, Han Jianping, Zhao Jiquan, Han Shuangzhan and Zhao Yanli(1. Department of Pharmaceutical engineering, Hebei university of Technology, Tianjin 300130China 2. Shijiazhuang Vitamin medicine limited Cor poration, Shijiazhuang Hebei ProvinceAbstract: The synthesis of glycerol trioleate from oleic acid and glycerol with toluene-p- sulfonic acidas catalyst was studied. The optimal conditions were obtained as follows: molar ratio of oleic acid toglycerol=1. 1: 1, w( catalyst)=6.9% of glycerol, reaction temperature 150-160C, reaction time4.5 h. The yield is 92. 7%. The methods for separating and analyzing glycerol trioleate were givenKey words: glycerol trioleate; oleic acid toluene- p- sulfonic acid中國煤化工CNMHG第6期胡云霞等.石油天然氣脫硫劑的研究351.4脫硫劑的實(shí)驗室評價(jià)方法異丙醇胺、乙醇胺的加入量各為0.1%時(shí),其硫容在一定直徑的吸附器中,裝入一定質(zhì)量的脫都達到各自的最大值,與未加添加劑的脫硫劑相硫劑,H2S以10mL/min的流速通入,并由鋼瓶比,硫容分別提高了62%,50%,40%和107%中的N2以250mL/s的流速帶入吸附器,未反應因此,選擇0.1%的乙醇胺為添加劑的H2S氣體由吸收液吸收,以無(wú)色澄清的堿性鋅表1添加劑種類(lèi)及用量對硫容的影響氨絡(luò )鹽吸收液變渾濁時(shí)作為吸附終點(diǎn),吸附結束添加劑硫容/(m后用分光光度計測吸收液的吸光度,計算吸硫容苦味酸鄰苯三酚二異丙醇胺乙醇胺量9.059.05硫容為單位質(zhì)量脫硫劑脫除的H2S換算成0,025單質(zhì)硫的質(zhì)量。硫容越大,單位質(zhì)量脫硫劑的脫14.6硫效果越好。硫容(g/g)=累計脫硫質(zhì)量15.6脫硫劑質(zhì)量1.011.92結果與討論2.1活性炭種類(lèi)對脫硫活性的影響分別用杏殼炭、煤制炭、椰殼炭進(jìn)行實(shí)驗。結2.5實(shí)驗氣中H2S含量對硫容的影響果表明:杏殼炭的脫硫效果最好,煤制炭次之,椰實(shí)驗發(fā)現,在固定實(shí)驗氣流速情況下,配制氣殼炭較差。但杏殼炭單價(jià)高,且與煤制炭的脫硫體中H2S含量從5g/m3增加到14g/m3時(shí),硫效果相差不多,所以以煤制炭為脫硫劑主料。容呈曲線(xiàn)遞減,即H2S含量每增加一倍,硫容減碳酸鈉溶液濃度對脫硫劑活性的影晌少10%~20%,可見(jiàn)降低H2S的濃度有利于脫硫反應。但為了縮短實(shí)驗周期,配制的實(shí)驗氣中H2S濃度遠大于需處理的石油天然氣中H2S的濃度(40~400mg/m3)2.6實(shí)驗氣流速對硫容的影響實(shí)驗氣流速對硫容的影響明顯,流速從300mL/min降到100mL/min時(shí),硫容提高20%30%。這是因為流速降低,增加了H2S與脫硫劑浸演液酸鈉含量.圖2碳酸鈉溶液濃度對硫容的影響的接觸時(shí)間,有利于H2S進(jìn)行物理和化學(xué)吸附用2%,5%,10%,20%碳酸鈉溶液浸漬經(jīng)過(guò)2.7脫硫劑質(zhì)量對硫容的影響干燥處理的活性炭,實(shí)驗結果表明:用5%碳酸鈉分別稱(chēng)取脫硫劑5.0,10.0g,在同樣的操作溶液浸漬活性炭脫硫效果最好。因為溶液濃度過(guò)條件下比較其脫硫效果。當脫硫劑的質(zhì)量增大到高不宜滲透進(jìn)粒狀催化劑微孔,導致活性組分分2倍時(shí),其脫硫能力相應超過(guò)了2倍多。這是因布不均;濃度過(guò)低,則需多次浸漬才能滿(mǎn)足負載為脫硫劑的質(zhì)量增大時(shí)吸附層的高徑比變大量。故選用5%碳酸鈉為宜H2S在床層里的停留時(shí)間延長(cháng),因此在實(shí)際生產(chǎn)2.3浸漬時(shí)間對脫硫劑活性的影晌中一次投放量越大越有利于脫硫分別用5%碳酸鈉溶液浸漬活性炭2,4,12脫硫性能中試評價(jià)和現場(chǎng)實(shí)驗24h。制備好以上脫硫劑后,經(jīng)評價(jià)得知浸漬12實(shí)驗地點(diǎn):克拉瑪依采油二廠(chǎng)2“氣站h以后,吸附達到平衡,因此浸漬時(shí)間選為12h3.1中型試驗2.4添加劑對脫硫劑活性的影響原料氣中H2S含量為240mg/m3;大氣溫度添加劑種類(lèi)和用量對硫容的影響見(jiàn)表1。從13℃;大氣壓力0.989MPa;天然氣流速25L表1可見(jiàn),隨添加劑苦味酸、鄰苯三酚、二異丙醇min;進(jìn)口壓力0.17MPa;A柱裝筆者研制的脫胺、乙醇胺的用量從0增加到1.%時(shí),硫容隨之硫劑100g;B柱裝市售脫硫劑B100g,分為兩個(gè)改變。當苦味酸的加入量為0.05%,鄰苯三酚系統同時(shí)進(jìn)行擊里爪主中國煤化工CNMHG細石油化表2中試結果取樣日期和時(shí)間通過(guò)各柱氣體流量出口含硫/(mg:m-3)脫H2S量/(g·100g-1)2002-04-10T10:062002-04-10T11:201850.71850.72450.769.1002-04-10T13:086584.26584.225.33.2專(zhuān)家現場(chǎng)實(shí)驗b.脫硫劑壽命由一次投放量、需處理的天然進(jìn)口壓力0.15MPa;原料氣中H2S含量為氣中H2S濃度及通氣速度決定。127.25mg/m3;脫硫劑質(zhì)量120.0g;天然氣流速c.經(jīng)現場(chǎng)實(shí)驗證明筆者研制的脫硫劑脫硫效52L/min,結果見(jiàn)表3。果比市售的脫硫劑脫硫效果好表3專(zhuān)家現場(chǎng)實(shí)驗結果d.該脫硫劑的一次使用壽命和再生方法,以活性炭樣品及物理吸附與化學(xué)吸附之間的關(guān)系有待進(jìn)一步研檢出H2S時(shí)H2S含量/(mg·m-3)9.8540.308究試驗天然氣體積/m31.42692.6377被吸附H2S的量/mg181,58335,65參考文獻活性炭吸附H2S量/(mg·g-1)21GB17820.天然氣,國家質(zhì)量技術(shù)監督局結論2 Turk A, Sakalls E, Lessuck J. et al. Aa Injection ena.以煤質(zhì)活性炭為載體,使用5%碳酸鈉溶液 hances capacity of activated carbon for hydrogen sulfide and作浸漬劑,0.1%的乙醇胺作添加劑,浸漬12h,常ethyl mercaptan [J]. Environ Sci Technol, 1989, 23(10)溫下可以有效脫除H2S。1241~1245RESEARCH ON DESULFURIZER FOR PETROLEUM NATURAL GASHu Yunxia 2, Yan Rengeng, Xi Huimin, Yang Tao, Zhang Xulong and Wang jide(1. College of Chemistry Chemical Engineering, Xinjiang University, Urumgi 830046, china2. Department of Chemistry, Yili Normal College, Yili 835000, China; 3. 2 Gas Station, No. 2Petroleum Production Factory, Kelana1000, China; 4. Jinye Company, Kelamayi 834000China)Abstract: A solid desulfurizer for natural gas was prepared from active carbon with ethanolamine asadditive and Na, CO3 as modified. The effects of the variety of active carbon and additives, the concentration of the impregnant and different preparation conditions on the sulfur capacity of the impregnatedactive carbon were investigated. The results showed that the optimal desulfurizer is composed of coalbased active carbon, impregnated with 5% Na, CO solution and 0. 1% ethanolamine as additive. Theproduct was tested by in situ experiment and identified by experts. This product is better than thoseKey words: modified active carbon; desulfurizer; adsorption; hydrogen sulfide中國煤化工CNMHG