CN108018095B - 一种适用于轻烃燃料中的新型脱硫剂 - Google Patents
一种适用于轻烃燃料中的新型脱硫剂 Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 34
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 33
- 239000000446 fuel Substances 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010457 zeolite Substances 0.000 claims abstract description 19
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 15
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 15
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010445 mica Substances 0.000 claims abstract description 15
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
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- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 7
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- 150000003568 thioethers Chemical class 0.000 abstract description 4
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- 239000002283 diesel fuel Substances 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 239000003502 gasoline Substances 0.000 description 1
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- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
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Abstract
本发明涉及轻烃原料净化研究技术领域,公开了一种适用于轻烃燃料中的新型脱硫剂,利用云母粉、高岭土作为催化氧化硫化物的基体,负载金属离子后改变了其内部的微孔结构,沸石与热塑弹性体结合,能够增强其力学强度,同时比表面积和孔结构都得到增大,二者混合高温制备粒径小至纳米级别的共混材料对硫化物的吸附作用极强,本发明制备的脱硫剂能够除去99.9%以上的含硫物质,并且能够带走苯、甲醇等有害物质,燃烧后只产生二氧化碳和水蒸汽。
Description
技术领域
本发明属于轻烃原料净化研究技术领域,具体涉及一种适用于轻烃燃料中的新型脱硫剂。
背景技术
“烃”就是碳、氢两种元素以不同的比例混合而成的一系列物质。其中较轻的部分,就叫做轻烃。天然气的主要成份是C1甲烷,含少量的C2乙烷,液化石油气的主要成份是C3丙烷、C4丁烷,它们在常温常压下呈气态,叫气态轻烃。C5-C16的烃在常温常压下是液态,我们就叫它液态轻烃。液态轻烃中最轻的部分是C5、C6,饱和的C5 、C6是鼓泡制气的最好原料,再重一点的部分就是汽油、煤油和柴油等。轻烃燃气与天然气一样,可作为一次能源替代液化气、柴油、电等二次能源,是工业企业能源改造理想气源。轻烃燃气已通过了国家环境保护监测部门的检测,国家环保部将该燃气项目认定为“国家重点环境保护实用技术推广项目”,建设部将该新型燃气列为“城市补充燃气”,在全国推广应用。
轻烃是轻烃燃气的原料,可以制成燃烧气体供热,我们通俗称为混空轻烃燃气,由于原料的纯净度不高,烧燃中伴随的副反应较多,原料如果不经过净化处理,会浪费能源的利用价值,且造成极大的污染,现有的脱硫剂在轻烃的脱硫率上效果并不显著。
发明内容
本发明的目的是针对现有的问题,提供了一种适用于轻烃燃料中的新型脱硫剂,能够除去99.9%以上的含硫物质,并且能够带走苯、甲醇等有害物质,燃烧后只产生二氧化碳和水蒸汽。
本发明是通过以下技术方案实现的:
一种适用于轻烃燃料中的新型脱硫剂,按照重量份计由以下成分制成:云母粉25-30份、高岭土15-25份、沸石30-40份、硝酸铜3.5-4.5份、氢氧化钠溶液3.0-4.0份、氯化钠1.5-2.5份、热塑性聚氨酯45-55份、四氢呋喃60-70份、去离子水200-240份,制备方法包括以下步骤:
(1)将云母粉、高岭土粉碎至100-120目,加入2-3倍体积的去离子水,混合搅拌30-40分钟,加入占体系体积20-25%的无水乙醇,加热至40-50℃,超声分散8-10分钟,继续加热至70-80℃,在300-350转/分钟的搅拌速度下滴加氢氧化钠溶液,滴加完后继续反应2-3小时;
(2)将硝酸铜、氯化钠溶解在剩余的去离子水中,加热至100℃,沸石研磨至粉料后投入到沸水中加热水煮3-5小时,冷却后过滤,在50-60℃烘箱中干燥5-6小时,将热塑弹性体与四氢呋喃混合溶解,加热至60-70℃,搅拌至粘稠液,将干燥后的沸石加入到粘稠液中,在30-40℃下固化反应4-6小时;
(3)将步骤(1)中的反应物和步骤(2)中的固化物混合,加入到反应釜中,设定反应温度为200-220℃,反应时间为15-18小时,反应结束后自然降温,得到产物使用无水乙醇和去离子水分别清洗3-5遍,在70-80℃烘箱中干燥至恒重即可。
作为对上述方案的进一步描述,所述脱硫剂在轻烃燃料中的使用量为15-20克/立方米。
作为对上述方案的进一步描述,步骤(1)所述使用的氢氧化钠溶液质量浓度为45-50%,滴加速度在40-50滴/分钟范围。
作为对上述方案的进一步描述,该脱硫剂在30-300℃温度下均可使用。
本发明相比现有技术具有以下优点:为了解决现有轻烃原料中使用的脱硫剂脱硫效果不佳的问题,本发明提供了一种适用于轻烃燃料中的新型脱硫剂,利用云母粉、高岭土作为催化氧化硫化物的基体,负载金属离子后改变了其内部的微孔结构,沸石与热塑弹性体结合,能够增强其力学强度,同时比表面积和孔结构都得到增大,二者混合高温制备粒径小至纳米级别的共混材料对硫化物的吸附作用极强,本发明制备的脱硫剂能够除去99.9%以上的含硫物质,并且能够带走苯、甲醇等有害物质,燃烧后只产生二氧化碳和水蒸汽。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
实施例1
一种适用于轻烃燃料中的新型脱硫剂,按照重量份计由以下成分制成:云母粉25份、高岭土15份、沸石30份、硝酸铜3.5份、氢氧化钠溶液3.0份、氯化钠1.5份、热塑性聚氨酯45份、四氢呋喃60份、去离子水200份,制备方法包括以下步骤:
(1)将云母粉、高岭土粉碎至100目,加入2倍体积的去离子水,混合搅拌30分钟,加入占体系体积20%的无水乙醇,加热至40℃,超声分散8分钟,继续加热至70℃,在300转/分钟的搅拌速度下滴加氢氧化钠溶液,滴加完后继续反应2小时;
(2)将硝酸铜、氯化钠溶解在剩余的去离子水中,加热至100℃,沸石研磨至粉料后投入到沸水中加热水煮3小时,冷却后过滤,在50℃烘箱中干燥5小时,将热塑弹性体与四氢呋喃混合溶解,加热至60℃,搅拌至粘稠液,将干燥后的沸石加入到粘稠液中,在30℃下固化反应4小时;
(3)将步骤(1)中的反应物和步骤(2)中的固化物混合,加入到反应釜中,设定反应温度为200℃,反应时间为15小时,反应结束后自然降温,得到产物使用无水乙醇和去离子水分别清洗3遍,在70℃烘箱中干燥至恒重即可。
作为对上述方案的进一步描述,所述脱硫剂在轻烃燃料中的使用量为15克/立方米。
作为对上述方案的进一步描述,步骤(1)所述使用的氢氧化钠溶液质量浓度为45%,滴加速度在40-50滴/分钟范围。
作为对上述方案的进一步描述,该脱硫剂在30-300℃温度下均可使用。
实施例2
一种适用于轻烃燃料中的新型脱硫剂,按照重量份计由以下成分制成:云母粉28份、高岭土20份、沸石35份、硝酸铜4.0份、氢氧化钠溶液3.5份、氯化钠2.0份、热塑性聚氨酯50份、四氢呋喃65份、去离子水220份,制备方法包括以下步骤:
(1)将云母粉、高岭土粉碎至110目,加入2.5倍体积的去离子水,混合搅拌35分钟,加入占体系体积22%的无水乙醇,加热至45℃,超声分散9分钟,继续加热至75℃,在330转/分钟的搅拌速度下滴加氢氧化钠溶液,滴加完后继续反应2.5小时;
(2)将硝酸铜、氯化钠溶解在剩余的去离子水中,加热至100℃,沸石研磨至粉料后投入到沸水中加热水煮4小时,冷却后过滤,在55℃烘箱中干燥5.5小时,将热塑弹性体与四氢呋喃混合溶解,加热至65℃,搅拌至粘稠液,将干燥后的沸石加入到粘稠液中,在35℃下固化反应5小时;
(3)将步骤(1)中的反应物和步骤(2)中的固化物混合,加入到反应釜中,设定反应温度为210℃,反应时间为16小时,反应结束后自然降温,得到产物使用无水乙醇和去离子水分别清洗4遍,在75℃烘箱中干燥至恒重即可。
作为对上述方案的进一步描述,所述脱硫剂在轻烃燃料中的使用量为18克/立方米。
作为对上述方案的进一步描述,步骤(1)所述使用的氢氧化钠溶液质量浓度为48%,滴加速度在40-50滴/分钟范围。
作为对上述方案的进一步描述,该脱硫剂在30-300℃温度下均可使用。
实施例3
一种适用于轻烃燃料中的新型脱硫剂,按照重量份计由以下成分制成:云母粉30份、高岭土25份、沸石40份、硝酸铜4.5份、氢氧化钠溶液4.0份、氯化钠2.5份、热塑性聚氨酯55份、四氢呋喃70份、去离子水240份,制备方法包括以下步骤:
(1)将云母粉、高岭土粉碎至120目,加入3倍体积的去离子水,混合搅拌40分钟,加入占体系体积25%的无水乙醇,加热至50℃,超声分散10分钟,继续加热至80℃,在350转/分钟的搅拌速度下滴加氢氧化钠溶液,滴加完后继续反应3小时;
(2)将硝酸铜、氯化钠溶解在剩余的去离子水中,加热至100℃,沸石研磨至粉料后投入到沸水中加热水煮5小时,冷却后过滤,在60℃烘箱中干燥6小时,将热塑弹性体与四氢呋喃混合溶解,加热至70℃,搅拌至粘稠液,将干燥后的沸石加入到粘稠液中,在40℃下固化反应6小时;
(3)将步骤(1)中的反应物和步骤(2)中的固化物混合,加入到反应釜中,设定反应温度为220℃,反应时间为18小时,反应结束后自然降温,得到产物使用无水乙醇和去离子水分别清洗5遍,在80℃烘箱中干燥至恒重即可。
作为对上述方案的进一步描述,所述脱硫剂在轻烃燃料中的使用量为20克/立方米。
作为对上述方案的进一步描述,步骤(1)所述使用的氢氧化钠溶液质量浓度为50%,滴加速度在40-50滴/分钟范围。
作为对上述方案的进一步描述,该脱硫剂在30-300℃温度下均可使用。
Claims (4)
1.一种适用于轻烃燃料中的新型脱硫剂,其特征在于,按照重量份计由以下成分制成:云母粉25-30份、高岭土15-25份、沸石30-40份、硝酸铜3.5-4.5份、氢氧化钠溶液3.0-4.0份、氯化钠1.5-2.5份、热塑性聚氨酯45-55份、四氢呋喃60-70份、去离子水200-240份,制备方法包括以下步骤:
(1)将云母粉、高岭土粉碎至100-120目,加入2-3倍体积的去离子水,混合搅拌30-40分钟,加入占体系体积20-25%的无水乙醇,加热至40-50℃,超声分散8-10分钟,继续加热至70-80℃,在300-350转/分钟的搅拌速度下滴加氢氧化钠溶液,滴加完后继续反应2-3小时;
(2)将硝酸铜、氯化钠溶解在剩余的去离子水中,加热至100℃,沸石研磨至粉料后投入到沸水中加热水煮3-5小时,冷却后过滤,在50-60℃烘箱中干燥5-6小时,将热塑性聚氨酯与四氢呋喃混合溶解,加热至60-70℃,搅拌至粘稠液,将干燥后的沸石加入到粘稠液中,在30-40℃下固化反应4-6小时;
(3)将步骤(1)中的反应物和步骤(2)中的固化物混合,加入到反应釜中,设定反应温度为200-220℃,反应时间为15-18小时,反应结束后自然降温,得到产物使用无水乙醇和去离子水分别清洗3-5遍,在70-80℃烘箱中干燥至恒重即可。
2.如权利要求1所述一种适用于轻烃燃料中的新型脱硫剂,其特征在于,所述脱硫剂在轻烃燃料中的使用量为15-20克/立方米。
3.如权利要求1所述一种适用于轻烃燃料中的新型脱硫剂,其特征在于,步骤(1)所述使用的氢氧化钠溶液质量浓度为45-50%,滴加速度在40-50滴/分钟范围。
4.如权利要求1所述一种适用于轻烃燃料中的新型脱硫剂,其特征在于,该脱硫剂在30-300℃温度下均可使用。
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