2003年11精細(xì)石油化工SPECIALITY PETROCHEMICALS第6期石油天然氣脫硫劑的研究胡云霞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835003.克拉瑪依采油二廠2號(hào)氣站,克拉瑪依834000;4.克拉瑪依金葉公司,克拉瑪依8340000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、改性劑及添加劑的含量以及不同制備條件對(duì)活性炭脫硫活性能的影響。結(jié)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(xiàn)場(chǎng)專家鑒定,其脫硫性能優(yōu)于市售同類產(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?cè)噭┯?。新疆油田公司的彩南油?*氣站和石西油721分光光度度計(jì)。田的天然氣中含硫量均超過(guò)國(guó)家標(biāo)準(zhǔn)規(guī)定的201.2脫硫劑的制備mg/m,氣站現(xiàn)用的市售脫硫劑價(jià)格及運(yùn)輸成取一定量的煤制炭用蒸餾水煮沸,洗凈后,在本較高,為此筆者開發(fā)了一種新脫硫劑110℃烘4h,然后用一定濃度的碳酸鈉溶液及活性炭應(yīng)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10℃烘干12h,直至干燥。究較多,主要集中在脫硫機(jī)理及添加活性組分的1.3脫硫劑的實(shí)驗(yàn)室評(píng)價(jià)裝置研究上。在活性炭中添加適當(dāng)?shù)母男詣┛梢燥@著硫化氫入口本底取樣口增強(qiáng)活性炭的吸附性能,從而既可降低活化能,混合器可以提高硫容2。轉(zhuǎn)子流量讠I實(shí)驗(yàn)光度法分析吸收瓶吸附器1.1主要試劑與儀器圖1脫硫劑的實(shí)驗(yàn)室評(píng)價(jià)裝置脫硫劑B:2108干脫硫劑;煤制炭,新疆昌吉萬(wàn)名活性炭廠;對(duì)氨基二甲苯胺鹽酸鹽,CR;收稿日期:2002-10-22;修改穡收到日期: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)Na2CO3、鄰苯三酚、乙二胺、苦味酸、乙醇胺、二異的研究工作,Emi: I wangid( xiu,du.cnSTUDY ON SYNTHESIS OF GLYCEROL TRIOLEATEZhang Yuecheng, Hu Qiuyi, Han Jianping, Zhao Jiquan, Han Shuangzhan and Zhao Yanli2(l. Department of Pharmaceutical Engineering, Hebei University of Technology, Tianjin 300130China; 2. Shijiazhuang Vitamin medicine Limited Cor poration, Shijiazhuang Hebei ProvinceShijiazhuang 050035, China)Abstract: 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 150-160 C, reaction tim4.5 h. The yield is 92. 7%. The methods for separating and analyzing glycerol trioleate were givenKey words: glycerol trioleate; oleic acid; toluene-p-sulfcnic acl6胡云霞等.石油天然氣脫硫劑的研究1.4脫硫劑的實(shí)驗(yàn)室評(píng)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,裝人一定質(zhì)量的脫都達(dá)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(yīng)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添加劑種類及用量對(duì)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(jié)束添加劑硫容/(mg:g1)后用分光光度計(jì)測(cè)吸收液的吸光度,計(jì)算吸硫容用量,%苦味酸鄰苯三酚二異丙醇胺乙醇胺量9.059.059.05硫容為單位質(zhì)量脫硫劑脫除的H2S換算成單質(zhì)硫的質(zhì)量。硫容越大,單位質(zhì)量脫硫劑的脫9.1414.6硫效果越好18.8硫容(g/s)=累計(jì)脫硫質(zhì)量15.6脫硫劑質(zhì)量1.011.09.1011.92結(jié)果與討論2.1活性炭種類對(duì)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(yàn)。結(jié)2.5實(shí)驗(yàn)氣中H2S含量對(duì)硫容的影響果表明:杳殼炭的脫硫效果最好,煤制炭次之,椰實(shí)驗(yàn)發(fā)現(xiàn),在固定實(shí)驗(yàn)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HS含量從5g/m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遞減,即H2S含量每增加一倍,硫容減2.2碳酸鈉溶液濃度對(duì)脫硫劑活性的影響少10%~20%,可見降低H2S的濃度有利于脫硫反應(yīng)。但為了縮短實(shí)驗(yàn)周期,配制的實(shí)驗(yàn)氣中H2S濃度遠(yuǎn)大于需處理的石油天然氣中H2S的濃度(40~400mg/m3)。2.6實(shí)驗(yàn)氣流速對(duì)硫容的影響實(shí)驗(yàn)氣流速對(duì)硫容的影響明顯,流速?gòu)?00mL/min降到100mL/min時(shí),硫容提高20%30%。這是因?yàn)榱魉俳档?增加了H2S與脫硫劑浸漬液酸鈉含量.微圖2碳酸鈉溶液濃度對(duì)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)27脫硫劑質(zhì)量對(duì)硫容的影響干燥處理的活性炭,實(shí)驗(yàn)結(jié)果表明:用5%碳酸鈉分別稱取脫硫劑5.0,10.0g,在同樣的操作溶液浸漬活性炭脫硫效果最好。因?yàn)槿芤簼舛冗^(guò)條件下比較其脫硫效果。當(dāng)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(dǎo)致活性組分分2倍時(shí),其脫硫能力相應(yīng)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足負(fù)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(zhǎng),因此在實(shí)際生產(chǎn)2.3浸潰時(shí)間對(duì)脫硫劑活性的影響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2,4,12,3脫硫性能中試評(píng)價(jià)和現(xiàn)場(chǎng)實(shí)驗(yàn)24h。制備好以上脫硫劑后,經(jīng)評(píng)價(jià)得知浸漬12實(shí)驗(yàn)地點(diǎn):克拉瑪依采油二廠2氣站h以后,吸附達(dá)到平衡,因此浸漬時(shí)間選為12h3.1中型試驗(yàn)2.4添加劑對(duì)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和用量對(duì)硫容的影響見表1。從13℃;大氣壓力0.989MPa;天然氣流速25L表1可見,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(dāng)苦味酸的加入量為0.05%,鄰苯三酚系統(tǒng)同時(shí)進(jìn)行試驗(yàn),結(jié)果見表2。精細(xì)石油化工表2中試結(jié)果取樣日期和時(shí)間通過(guò)各柱氣體流量/L出口含硫/(mg·m-3)脫H2S量/(g·100g-1)002-04-10T10:06200204-10T11:001570.7無(wú)含硫2002-04-10T11:201850.71850.72002-04-10T11:3050.72450.715.269.12002-04-10T13:086584.26584,225.398.93.2專家現(xiàn)場(chǎng)實(shí)驗(yàn)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(xiàn)場(chǎng)實(shí)驗(yàn)證明筆者研制的脫硫劑脫硫效52L/min,結(jié)果見表3。果比市售的脫硫劑脫硫效果好。表3專家現(xiàn)場(chǎng)實(shí)驗(yàn)結(jié)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(yàn)天然氣體積/m31.42692.6377被吸附H2S的量/mg181,58335,65活性炭吸附H2S量/(mg·g-1)1.512.801GB17820.天然氣,國(guó)家質(zhì)量技術(shù)監(jiān)督局結(jié)論2 Turk A, Sakalls E, Lessuck J, et al. Ammonia injection en-a.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 methyl mercaptan[J. Environ Sci technol,1989,23(10溫下可以有效脫除H2S1241~1245RESEARCH 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, Kelamayi 834000, China; 4. Jinye Company, Kelamayi 834000Abstract: A solid desulfurizer for natural gas was prepared from acadditive and Nay CO, as modified. The effects of the variety of active carbon and additives, the concentration of the impregnant and different preparation conditioactive carbon were investigated. The results showed that the optimal desulfurizer is composed of coal-based 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