CN105623711B - 一种以SiO2‑NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法 - Google Patents
一种以SiO2‑NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
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- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 229910052681 coesite Inorganic materials 0.000 claims abstract description 13
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 238000004073 vulcanization Methods 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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Classifications
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/201—Impurities
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Abstract
一种以SiO2‑NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,属于燃料油加工技术领域。将SiO2‑NiO复合气凝胶填装入固定床吸附装置中,在一定空速下,通入含有噻吩或苯并噻吩的模拟汽油。并在反应器的下端出口处收集吸附后的模拟汽油,进行气相色谱分析,结果表明SiO2‑NiO复合气凝胶对噻吩与苯并噻吩有良好的吸附性能。本发明的SiO2‑NiO复合气凝胶吸附剂制备简单,成本低廉,该吸附剂可多次重复使用,操作方便、环境友好、经济效益高,且其吸附条件温和、对吸附设备的要求低。
Description
技术领域
本发明属于燃料油加工技术领域,具体涉及一种以π络合吸附的SiO2-NiO复合气凝胶脱硫吸附剂及其制备方法和在汽油脱硫中的应用。
背景技术
近年来各国对环境保护的重视,对燃料油中的硫含量提出了严格的限量标准。欧盟国家从2010年起,燃料油中的硫含量必须小于10μg/g。在燃料电池方面,燃料油的硫化物会使电池电极的催化剂中毒,因此其燃料油的硫含量必须低于0.1μg/g。现在的工业生产中,脱硫的主要工艺仍是传统的加氢脱硫,但其操作成本较高、耗氢量大、操作条件苛刻,降低汽油中辛烷值等缺点。且加氢脱硫只对于硫醇、硫醚、无机硫等有较好效果,对于热稳定性极高的噻吩类硫化物的脱硫效果很差。吸附脱硫由于其成本低廉,操作条件温和,脱硫效果好,不污染环境,其中π络合吸附脱硫相对于物理吸附脱硫是有选择性的,对于化学吸附脱硫更易于脱附再生,是目前最有前景的脱硫方法。
π络合吸附脱硫的关键在于制备一种高效的π络合吸附剂。在所有d区金属元素中,均具有(n-1)d10ns0的电子构型,既容易接受电子,也极易给予过多的d电子,与硫化物形成π络合吸附,常用于制备π络合脱硫吸附剂的金属离子有Cu2+、Ag+、Ni2+、Co2+等。而制备π络合脱硫吸附剂,须将这些金属离子分散在高比表面积的载体上。根据π络合脱硫吸附剂载体不同,可将π络合脱硫吸附剂分为以下几种:
以分子筛为载体的π络合脱硫吸附剂。沈阳化工大学(公开号 CN 103170305 A)以负载Ag离子的13X分子筛为脱硫吸附剂,用于深度脱除汽油中的噻吩及其衍生物和苯并噻吩。其中银的元素含量占吸附剂总重量的3%~5%,银元素为离子态。中国科学院(公开号 CN1511629 A)制备了一种深度脱除硫化物的分子筛吸附剂,由Y型分子筛负载金属盐类组成。该吸附剂对硫的吸附容量可达65mg硫/g吸附剂。这类π络合吸附剂,载体价格低廉,制备方法简单,可循环再生。但微孔分子筛脱硫吸附剂所交换的过渡金属离子数目有限,对硫化物的吸附容量不大,且微孔分子筛自身的微孔结构,大分子的噻吩类硫化物由于分子尺寸效应无法进入孔道内与金属离子形成π络合作用,即无法达到深度脱硫。
以活性炭为载体的π络合脱硫吸附剂。沈阳化工大学(公开号 CN 103143322 A)制备了一种负载了Fe离子的活性炭吸附剂,对汽油中的噻吩及其衍生物有较大的吸附容量与选择性,且制备方法简单,再生容易,吸附剂使用寿命长。中国石油化工股份有限公司(公开号 CN 104549143 A)通过采用含Al、Zn、Ni等金属的盐和H3PO4作为助剂对活性炭进行修饰改性,较好地解决了气体原料吸附净化脱硫技术中存在单一吸附剂不能同时有效脱除多种硫化物、硫的脱除率低以及脱硫剂的穿透硫容低等问题。但活性炭的孔结构以微孔为主,改性的活性炭对噻吩类大分子硫化物的吸附容量仍然非常小,难以满足工业生产的要求。
以金属氧化物为载体的π络合脱硫吸附剂。南通大学(公开号 CN 10300787 A)以铜元素掺杂的介孔γ-Al2O3与含硫的燃料油接触,利用吸附法实现脱硫,操作成本低,吸附容量大,且再生方便。中国石油化工股份有限公司(公开号 CN 10161923 A)制备了一种脱硫吸附剂,该吸附剂包括以氧化铝为粘结剂,氧化锌为载体,再与络合剂溶液接触,然后负载金属促进剂。用于燃料油脱硫,活性高,吸附硫容量大。但在制备过程中,金属离子容易堵塞金属氧化物孔道,导致负载的活性组分在表面堆积,无法进入孔道内提供活性位,降低吸附脱硫性能,且此法较难应用于工业化生产。
发明内容
针对现有π络合吸附剂在脱除汽油中噻吩类硫中存在的上述问题,本发明的目的在于提供一种吸附条件温和、操作方便、吸附性能优越且吸附容量大、易再生的SiO2-NiO复合气凝胶作为π络合吸附剂,来脱除汽油中噻吩类硫的方法。
所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,其特征在于以SiO2-NiO复合气凝胶为吸附剂,将该吸附剂填装入固定床吸附装置中,在温度为0~100 ℃,以1~10 h-1的空速通入含有噻吩类硫的模拟汽油,经吸附后得到无硫的模拟汽油。
所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,其特征在于所吸附的噻吩类硫为噻吩或苯并噻吩。
所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,其特征在于SiO2-NiO复合气凝胶吸附剂以硅源和镍源为原料,采用溶胶凝胶-常压干燥法制备得到。
所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,其特征在于SiO2-NiO复合气凝胶吸附剂的制备方法如下:将乙醇、硅源、H2O与镍源的混合溶液在剧烈搅拌下混合均匀,加入氨水调节pH值至6.5,室温下静置得SiO2-NiO复合醇凝胶,常温条件下老化,再在无水乙醇/正硅乙酸酯混合溶剂中继续老化,以增强凝胶的骨架结构,再用正己烷对凝胶进行溶剂置换,除去凝胶中的乙醇、水、乙酸及其他有机分子,干燥得SiO2-NiO复合气凝胶。
所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,其特征在于所述硅源为正硅酸乙酯或水玻璃,优选为正硅酸乙酯;镍源为硝酸镍或醋酸镍,优选为硝酸镍。
所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,其特征在于SiO2-NiO复合气凝胶吸附剂中硅、镍摩尔比为5~200 : 1,优选为6~90: 1。
所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,其特征在于通入含噻吩或苯并噻吩的模拟汽油的空速为1~5 h-1,吸附温度为0~40 ℃。
所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,其特征在于所吸附处理的模拟汽油中的噻吩或苯并噻吩硫浓度为100~2000 ppm,优选为100~500 ppm。
所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的新方法,其特征在于SiO2-NiO复合气凝胶SiO2-NiO的孔径为5~20 nm,孔隙率为85~99%,比表面积为600~1500 m2/g。
通过采用上述技术,与现有技术相比,本发明的有益效果如下:
1)本发明的SiO2-NiO复合气凝胶具有典型介孔特征孔径(5~20 nm),高孔隙率(85~99%),高比表面积(600~1500 m2/g)等独特物理化学性质,因此噻吩类硫化物可无阻碍地进入气凝胶孔道内,活性组分与硫化物能充分接触,提高其吸附效率,将SiO2-NiO复合气凝胶作为π络合吸附剂,对噻吩类硫化物有良好的吸附性能,再生后仍然有良好的吸附性能;
2)本发明的SiO2-NiO复合气凝胶作为π络合脱硫吸附剂,其结构是由纳米级骨架颗粒构成,使骨架内的活性组分可充分暴露,在气凝胶的合成过程中,可将具有π络合作用的过渡金属盐加入其中,因此活性组分的量是可调节的;
3)本发明的吸附反应在常压下进行、吸附条件温和、对吸附设备的要求低、操作方便,且对噻吩类化合物有良好的吸附效果。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
SiO2-NiO复合气凝胶吸附剂的制备:本发明以硅镍摩尔比为60的SiO2-NiO复合气凝胶吸附剂为例,其制备方法如下:
将15 mL EtOH、5 mL TEOS、3mL H2O与0.24g硝酸镍的混合溶液在剧烈搅拌下混合均匀,加入氨水调节pH值至6.5,室温下静置约15 min得SiO2-NiO复合醇凝胶,在常温条件下老化48 h后,再在体积比为10:1的无水乙醇/正硅乙酸酯中老化48 h,以增强凝胶的骨架结构,再用正己烷对凝胶进行溶剂置换,48 h内更换两次溶剂,除去凝胶中的乙醇,水,乙酸,及其他有机分子。最后150 ℃下干燥2 h,得硅镍摩尔比为60的SiO2-NiO复合气凝胶,该制备方法中,在其它条件不变的情况下改变硝酸镍的量即可得不同硅镍摩尔比的SiO2-NiO复合气凝胶。
实施例1-4:不同硅源与镍源的SiO2-NiO复合气凝胶对吸附模拟汽油中噻吩类硫化物的影响
在采用溶胶-凝胶法制备的SiO2-NiO复合气凝胶中,所用的硅源有正硅酸乙酯、水玻璃,镍源有硝酸镍、醋酸镍。将制备完成的SiO2-NiO复合气凝胶进行穿透吸附脱硫实验,具体操作如下:在固定床反应器中,最底层填装适量的脱脂棉,然后填装1 g的SiO2-NiO气凝胶与适量的石英砂。吸附实验开始前,用正庚烷充分润湿所填装的吸附剂。通入模拟汽油,在反应器的下端出口处收集吸附后的模拟汽油,进行气相色谱分析。所得到的噻吩与苯并噻吩的穿透吸附容量,结果见表1。
表1 不同硅源与镍源对吸附模拟汽油中噻吩类硫化物的影响
从表1可以看出,在合成SiO2-NiO复合气凝胶所用的硅源与镍源中,硅源选用正硅酸乙酯,镍源选用硝酸镍,所合成的SiO2- NiO复合气凝胶在穿透吸附实验中,对噻吩与苯并噻吩有最大的穿透吸附容量,因此优选硅源为正硅酸乙酯,镍源为硝酸镍。
实施例5-9:不同硅镍摩尔比的SiO2- NiO复合气凝胶对吸附模拟汽油中噻吩类硫化物的影响
选用硅镍摩尔比分别6、40、90、150、200的SiO2- NiO气凝胶,对模拟汽油中噻吩类硫化物进行穿透吸附实验。其穿透吸附实验操作同实施例1~4,吸附结果见表2。
表2 不同硅镍摩尔比对吸附模拟汽油中噻吩类硫化物的影响
从表2可以看出,总体来说,SiO2- NiO气凝胶随着硅镍摩尔比的减小即镍含量的增加,对噻吩与苯并噻吩的穿透吸附容量也随之增加,但当镍含量增加到硅镍摩尔比为6时,穿透吸附容量开始降低。在硅钴摩尔比小于90后,噻吩与苯并噻吩的穿透吸附容量基本不增加,因此优选硅钴摩尔比为6~90的SiO2- NiO气凝胶。
实施案例10~14:不同空速对SiO2- NiO复合气凝胶吸附模拟汽油中噻吩类硫化物的影响
选用硅镍摩尔比为40的SiO2- NiO复合气凝胶。在空速为1 h-1、3 h-1、5 h-1、8 h-1、10 h-1下,对模拟汽油中噻吩类硫化物进行穿透吸附实验。其穿透吸附实验操作同实施例1~4,吸附结果见表3。
表3 不同空速对吸附模拟汽油中噻吩类硫化物的影响
从表3可以看出,空速的减小,噻吩与苯并噻吩的穿透吸附容量会逐渐增大,当空速减小到5 h-1之后,对噻吩类硫化物的穿透吸附容量变化不大,因此优选空速为1~5 h-1。
实施案例15~19:不同吸附温度对SiO2-NiO复合气凝胶吸附模拟汽油中噻吩类硫化物的影响
选用硅镍摩尔比为40的SiO2-NiO复合气凝胶。吸附温度分别选为0℃、25℃、40℃、80℃、100℃,对模拟汽油中噻吩类硫化物进行穿透吸附实验。穿透吸附实验操作同实施例1~4,吸附结果见表4。
表4 不同吸附温度对吸附模拟汽油中噻吩类硫化物的影响
从表4可以看出,随着吸附温度的升高,噻吩与苯并噻吩的穿透吸附容量逐渐减小,在80℃之后,噻吩与苯并噻吩的吸附穿透容量非常小,表明在此温度下,被SiO2-NiO复合气凝胶吸附的噻吩与苯并噻吩已脱附。因此优先吸附温度为0~40℃。
实施案例20~23:不同硫浓度对SiO2-NiO复合气凝胶吸附模拟汽油中噻吩类硫化物的影响
选用硅镍摩尔比为40的SiO2-NiO复合气凝胶。模拟汽油中的噻吩或苯并噻吩的硫浓度分别为100ppm、500ppm、1000ppm、2000ppm,进行穿透吸附实验。穿透吸附操作同实施例1~4,吸附结果见表5。
表5 不同硫浓度对吸附模拟汽油中噻吩类硫化物的影响
从表5可以看出,模拟汽油中噻吩或苯并噻吩硫浓度的增大,SiO2-NiO复合气凝胶对噻吩与苯并噻吩穿透吸附容量呈下降的趋势,因此优选模拟汽油中噻吩或苯并噻吩硫浓度为100~500 ppm。
Claims (9)
1.一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的方法,其特征在于以SiO2-NiO复合气凝胶为吸附剂,将该吸附剂填装入固定床吸附装置中,在温度为0~100 ℃,以1~10 h-1的空速通入含有噻吩类硫的模拟汽油,经吸附后得到无硫的模拟汽油,所吸附的噻吩类硫为噻吩或苯并噻吩,SiO2-NiO复合气凝胶吸附剂以硅源和镍源为原料,采用溶胶凝胶-常压干燥法制备得到,SiO2-NiO复合气凝胶吸附剂的制备方法如下:将乙醇、硅源、H2O与镍源的混合溶液在剧烈搅拌下混合均匀,加入氨水调节pH值至6.5,室温下静置得SiO2-NiO复合醇凝胶,常温条件下老化,再在无水乙醇/正硅乙酸酯混合溶剂中继续老化,以增强凝胶的骨架结构,再用正己烷对凝胶进行溶剂置换,除去凝胶中的乙醇、水、乙酸及其他有机分子,干燥得SiO2-NiO复合气凝胶。
2.根据权利要求1所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的方法,其特征在于所述硅源为正硅酸乙酯或水玻璃;镍源为硝酸镍或醋酸镍。
3.根据权利要求1所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的方法,其特征在于所述硅源为正硅酸乙酯;镍源为硝酸镍。
4.根据权利要求1所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的方法,其特征在于SiO2-NiO复合气凝胶吸附剂中硅、镍摩尔比为5~200 : 1。
5.根据权利要求1所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的方法,其特征在于SiO2-NiO复合气凝胶吸附剂中硅、镍摩尔比为6~90: 1。
6.根据权利要求1所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的方法,其特征在于通入含噻吩或苯并噻吩的模拟汽油的空速为1~5 h-1,吸附温度为0~40℃。
7.根据权利要求1所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的方法,其特征在于所吸附处理的模拟汽油中的噻吩或苯并噻吩硫浓度为100~2000 ppm。
8.根据权利要求1所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的方法,其特征在于所吸附处理的模拟汽油中的噻吩或苯并噻吩硫浓度为100~500 ppm。
9.根据权利要求1所述的一种以SiO2-NiO复合气凝胶为吸附剂脱除汽油中噻吩类硫的方法,其特征在于SiO2-NiO复合气凝胶SiO2-NiO的孔径为5~20 nm,孔隙率为85~99%,比表面积为600~1500 m2/g。
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CN1151333A (zh) * | 1995-06-07 | 1997-06-11 | 菲利浦石油公司 | 吸附剂组合物 |
US6309537B1 (en) * | 1998-12-10 | 2001-10-30 | Institut Francais Du Petrole | Hydrotreating hydrocarbon feeds in an ebullating bed reactor |
US9433924B2 (en) * | 2009-11-09 | 2016-09-06 | Wayne State University | Metaloxide—ZrO2 catalysts for the esterification and transesterification of free fatty acids and triglycerides to obtain bio-diesel |
CN101804329A (zh) * | 2010-04-22 | 2010-08-18 | 南京工业大学 | 一种用于汽油脱硫的吸附剂及其制备方法和利用该吸附剂进行汽油脱硫的方法 |
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