CN1003520B - 重整原料油脱硫剂 - Google Patents
重整原料油脱硫剂 Download PDFInfo
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- CN1003520B CN1003520B CN87103035.7A CN87103035A CN1003520B CN 1003520 B CN1003520 B CN 1003520B CN 87103035 A CN87103035 A CN 87103035A CN 1003520 B CN1003520 B CN 1003520B
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- 238000002407 reforming Methods 0.000 title claims abstract description 33
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 26
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- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 17
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 17
- 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 17
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 32
- 229960004643 cupric oxide Drugs 0.000 claims description 16
- 235000003599 food sweetener Nutrition 0.000 claims description 16
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 16
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 16
- 239000003765 sweetening agent Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 238000001833 catalytic reforming Methods 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000002574 poison Substances 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 230000008092 positive effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 230000003245 working effect Effects 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 229960000355 copper sulfate Drugs 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- -1 sulphur compound Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
重整原料油脱硫剂,用于石油加工工业中脱除油品中微量硫化物的产品。本发明以铜、镍作活性组分,高岭土作载体,特别适用于重整原料油经预加氢蒸发脱水操作后的固定床脱硫工艺中脱除上游过程中残留的微量硫,使原料油的硫含量降低到0.5ppM以下,硫醇含量降到0.07ppM以下,具有脱硫活性高,使用寿命长,原料广泛,成本低,不产生“毒害”重整催化剂的物质等特点,对提高催化重整过程效率具有积极效果。
Description
催化重整工艺是生产芳烃,改善石脑油辛烷值的一种有效方法,为了提高过程效率,近年来开发了多种以铂为活性组份,以铼或其它组分为助剂的双(多)金属重整催化剂,由于双(多)金属重整催化剂对硫化合物很敏感,只要原料油中有微量硫化合物存在,就会导致催化剂“中毒”而降低活性及选择性,造成油液收率降低和催化剂使用寿命缩短,严重时造成停工。因此要保证催化重整工艺顺利进行,首先要满足原料油的含硫量小于0.5ppm以下。避免双(多)金属重整催化剂因原料油含硫量高而失去活性造成停工损失。
本发明提出的重整原料油脱硫剂,主要用于重整原料油经预加氢蒸发脱水操作后的固定床脱硫工艺中,脱除上游过程中残留的微量硫化物,使原料油硫含量降到0.5ppm以下的产品。
在该技术领域中,目前使用的重整原料油脱硫剂按所含活性组分分类有:以含锌为主的脱硫剂,以含镍为主的脱硫剂,以含铜为主的脱硫剂等三类。据已有技术〈硫对“3741”双金属催化剂运行影响的报告〉(催化重整通讯1984,№3 P68-80)所述,在操作温度为180℃时,使用含活性组分锌的“0703”脱硫剂能取到一定效果。但脱硫效率低,较难保证油品硫含量稳定地控制在0.5ppm以下,并会产生ZnCl2“毒害”催化重整催化剂。又据已有技术〈二期工程引进装置所附的非均相催化剂和吸附剂简况(一)〉(上海石油化工总厂1980.6.15.P3)所述,美国环球油品公司出口的含活性组分镍的ADS-11脱硫剂,能将进料油含硫量由1ppm脱除到0.5ppm以下,使用寿命一年,价格高而国内无货。又据已有技术〈U.S.P4113606〉所述,含活性组分铜的脱硫剂可以用于该过程,但未报导其脱硫水平及脱硫剂的铜流失情况。
鉴于上述已有技术存在的问题。本发明的目的是:发明一种用于重整原料油经预加氢蒸发脱水操作后的固定床脱硫工艺中,能脱除上游过程中残留微量硫化物的脱硫剂,它能使原料油含硫量下降到0.5ppm以下,脱硫活性好的特性,同时不产“毒害”重整催化剂的物质。本脱硫剂的制造工艺简单,使用寿命二年,原料易得,成本低。
本发明的重整原料油脱硫剂是以高岭土为载体,铜、镍或钼为活性组分,按一定比例用共混法混合后,经挤条成型,干燥,焙烧后制得的产品。
本发明的重整原料油脱硫剂的配比(按百分比计)铜含量(以氧化铜计)为25-70%,最好在30-55%;镍含量(以氧化镍计)为5-30%,最好在10-25%;高岭土含量为25-60%最好在30-50%。本脱硫剂的铜元素以氧化铜、碳酸铜、硫酸铜、氯化亚铜形式加入,最好以氧化铜或碳酸铜形式加入。镍元素以氧化镍、碳酸镍、硝酸镍形式加入,最好以氧化镍、碳酸镍形式加入,载体高岭土可在沉淀碳酸铜或沉淀碳酸镍时加入,最好在共混合时加入。
本发明的重整原料油脱硫剂制造方法是:
1.将上述氧化铜(碳酸铜、硫酸铜、氯化亚铜),氧化镍(碳酸镍、硝酸镍),高岭土等物料按一定百分比装入球磨罐球磨。
2.取出混合的原料加入蒸馏水捏合。
3.将捏合好的原料在挤条机上进行挤条,挤压规格为φ1.2毫米条状。
4.挤条后整型,转速300~350转/分,时间10~15分钟。
5.整型后在24小时内凉干,然后烘干。
6.将烘干产品在下列条件下活化:
活化完成后经自然冷却,即为本发明的重整原料油脱硫剂产品。
产品物理性能:
比表面:40-50米2/克,孔容:0.22-0.24毫升/克;
强度:3-5公斤/颗;颗粒直径:φ1.2毫米。
产品组成:
本发明的重整原料油脱硫剂在使用时先要进行还原,条件为:温度300±5℃;时间12小时以上;常压:介质H2+N2或H2+H2O蒸汽,氢气浓度1-20%。
本发明的重整原料油脱硫剂使用条件为:
操作温度:100-200℃
操作压力:0-15kgf/cm2
液空速:0-12h-1
本发明的重整原料油脱硫剂,在重整原料油经预加氢蒸发脱水操作后的固定床脱硫工艺中,使用效果是能将原料油含硫1ppm左右脱除到0.5ppm以下,具有比现使用的任一种脱硫剂脱硫效率高,活性好,不产生“毒害”催化剂的物质,使用寿命二年,原料广泛,成本低的特征。
本发明实施例(按百分比计)
例一:氧化铜∶氧化镍∶高岭土=25∶30∶45
例二:氧化铜∶氧化镍∶高岭土=35∶5∶60
例三:氧化铜∶氧化镍∶高岭土=50∶25∶25
例四:氧化铜∶氧化镍∶高岭土=55∶10∶35
例五:氧化铜∶氧化镍∶高岭土=45∶25∶30
例六:氧化铜∶氧化镍∶高岭土=70∶5∶25
例七:氧化铜∶氧化镍∶高岭土=30∶20∶50
最佳实施例∶氧化铜∶氧化镍∶高岭土=45∶20∶35
以上各实施例配方均按上述制造方法制造。产品即为本发明的重整原料油脱硫剂。其使用性能参见表1、2、3、4。
附表说明:
表1,表明重整原料油脱硫剂脱硫效率比含镍的ADS-11脱硫剂高。
表2,表明重整原料油脱硫剂脱硫效率比含锌的0703脱硫剂高。
表3,表明重整原料油脱硫剂硫容量9%时脱硫效率仍在95%以上,说明脱硫剂寿命长。
表4,表明重整原料油脱硫剂具有良好的脱除有机硫的特性随温度增高效率增高。
表1 重整原料油脱硫剂与ADS-11对比
注:“原料油”一栏;1为预加氢蒸发脱水前的油品,2为主要含有机硫的油品;3为主要含有机硫的油品,配制时低硫油品硫含量稍高些。
表2 重整原料油脱硫剂与0703对比
表3 重整原料油脱硫剂硫容试验
表4 重整原料油脱硫剂脱硫醇试验
Claims (4)
1、一种重整原料油脱硫剂,其特征是该脱硫剂含有氧化铜、氧化镍、高岭土,其含量为氧化铜∶氧化镍∶高岭土=25~70∶5~30∶25~60(百分比)。
2、根据权利要求1所述的重整原料油脱硫剂,其特征在于氧化铜∶氧化镍∶高岭土=30~55∶10~25∶30~50(百分比)。
3、根据权利要求2所述的重整原料油脱硫剂,其特征在于氧化铜∶氧化镍∶高岭土=45∶20∶35(百分比)。
4、根据权利要求3所述的重整原料油脱硫剂,其特征在于所说脱硫剂的比表面为40~50米2/克,孔容为0.22~0.24毫升/克,强度为3~5公斤/颗,颗粒直径为1.2毫米。
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CN87103035.7A CN1003520B (zh) | 1987-09-10 | 1987-09-10 | 重整原料油脱硫剂 |
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CN87103035A CN87103035A (zh) | 1988-03-02 |
CN1003520B true CN1003520B (zh) | 1989-03-08 |
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Cited By (1)
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CN1609427B (zh) * | 2003-10-17 | 2011-12-28 | 通用电气公司 | 膜式冷却燃气轮机燃烧器的方法和装置 |
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US6274533B1 (en) * | 1999-12-14 | 2001-08-14 | Phillips Petroleum Company | Desulfurization process and novel bimetallic sorbent systems for same |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN1609427B (zh) * | 2003-10-17 | 2011-12-28 | 通用电气公司 | 膜式冷却燃气轮机燃烧器的方法和装置 |
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