CN104342200B - 一种重整生成油选择性加氢的方法 - Google Patents

一种重整生成油选择性加氢的方法 Download PDF

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CN104342200B
CN104342200B CN201310345116.4A CN201310345116A CN104342200B CN 104342200 B CN104342200 B CN 104342200B CN 201310345116 A CN201310345116 A CN 201310345116A CN 104342200 B CN104342200 B CN 104342200B
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oil
palladium
catalyst
sulfide
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CN104342200A (zh
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邵文
李学宽
栗雪云
吕占军
任建生
杜明仙
刘传强
周立功
杨英
朱颖
黄丙耀
李小平
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Petrochina Co Ltd
China Petroleum Engineering and Construction Corp
CNPC EastChina Design Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C10G2300/705—Passivation
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

本发明涉及一种重整生成油选择性加氢的方法；重整生成油，溴指数为7270mgBr/100g油，芳烃重量66.83%，反应条件:170℃、1.6MPa、4h-1、氢/油(V)200；其特征在于：使用的催化剂是含0.3%重量钯的Pd/γ-Al2O3，催化剂在装填前经含硫化合物二甲二硫、甲基硫醚、丁基硫醇或硫化氢干法钝化；硫化物钝化的加入量为钯硫摩尔比1-3.5；钝化温度为常温～230℃；使用这种钝化方法可以降低污染，减少投资，方便开工，钯催化剂经过硫化物钝化后，经过加氢精致的产品芳烃损失低于0.5（重）%，经过短时间反应后产品溴指数低于100，可以满足芳烃抽提对原料的要求。

Description

一种重整生成油选择性加氢的方法
技术领域：
本发明涉及一种重整生成油选择性加氢的方法。
背景技术：
钯系催化剂经常在不饱和烃类催化加氢中使用，已经授权的发明专利CN86108622和CN97118845.9就是Pd/γ-Al2O3用于重整生成油选择性加氢过程，该选择性加氢过程要求烯烃深度脱除，芳烃加氢损失小于0.5%。
重整生成油是石脑油经过Pt系催化剂在高温下反应生成芳烃的产品，含有大量芳烃，少量烷烃和烯烃。由于原料或生产工艺的差别重整生成油的组成一般是：芳烃含量50-85%、烷烃20-50%、烯烃3-15%。为了生产高纯度的芳烃，重整生成油选择性加氢要求把烯烃加氢脱除，加氢产品中溴指数低于100mgBr/100g油，芳烃加氢损失不能高于0.5%。发明专利CN86108622和CN97118845.9公开的选择性加氢反应的条件是：反应温度150-300℃、氢气分压0.5-3.0MPa、液体快速3-15h-1、氢油体积比100-500。
由于新鲜的钯催化剂初活性很高，在上述反应条件对重整生成油加氢选择性加氢，芳烃损失是很严重的。为了不让芳烃加氢损失，工业上一般使用芳烃和烯烃都很低的溶剂油配硫化物进行催化剂钝化处理，用于催化剂钝化的硫化物一般使用二甲二硫。钝化后的催化剂就只对烯烃有加氢活性，对芳烃没有加氢活性，避免了芳烃损失。无论是发明专利CN86108622和CN97118845.9还是已经发表的科研论文，都没有涉及重整生成油选择性加氢Pd/γ-Al2O3的钝化方法。
对于一个新开工的重整生成油选择性加氢装置，需要购买大量低芳烃、低烯烃的溶剂油作为钝化剂的载体油，这种钝化方法操作复杂，延长了开工时间，而且这些载体溶剂油使用后含有硫化物，污染环境，处理困难。如果不进行催化剂钝化，由于芳烃加氢发热，反应温度无法控制，有可能引起反应器飞温。在工业装置中要添加专门为钝化安装的管线和泵、阀，增加了投资。企业急需一种不使用载体油的干法Pd/γ-Al2O3催化剂钝化方法。本发明的Pd/γ-Al2O3干法钝化工艺解决了困扰企业多年的这一难题。
发明内容
本发明的目的是提供一种重整生成油选择性加氢的方法；本方法使用的催化剂的钯含量与发明专利CN86108622和CN97118845.9相同或相似，具体制备方法与物化性质参看上述两份专利。
本发明所述的用于选择性加氢的钯催化剂干法钝化的方法：
该选择性加氢催化剂为Pd/γ-Al2O3。
这种干法钝化使用的钝化剂是含硫的化合物，含硫化合物可以是二甲二硫、甲基硫醚、丁基硫醇或硫化氢。
使用这些硫化物钝化的加入量为钯硫摩尔比1-3.5之间。
钝化温度为常温到230℃。
本发明的优点是：
1、干法钝化，不使用载体油，降低了成本和硫化物污染。
2、操作简单而且容易控制，缩短了开工时间。
3、简化了流程，降低了投资。
具体实施方式
没有特殊说明，下面实施例的反应条件:170℃、1.6MPa、4h-1、氢/油(V)200。使用的催化剂是含0.3%钯的Pd/γ-Al2O3，原料是取自某厂的连续重整生产的重整生成油，溴指数为7270mgBr/100g油，芳烃含量66.83（重）%，下面实例都是使用这个原料，一般将不再标出其溴指数与芳烃含量。
实施例1，
从表1可以看出，未钝化的新鲜催化剂对芳烃、烯烃加氢都有很高的活性，芳烃损失严重。对于新鲜催化剂的开工，必须进行催化剂钝化。
表1、新鲜催化剂还原后未钝化的加氢结果
反应条件:170℃、1.6MPa、4h-1、氢/油(V)200
实施例2
干法钝化进入量对钝化效果影响比较大，表2是不同二甲二硫加入量的比较。钝化条件是170℃、常压、催化剂装填量50毫升、氢气流量20升/小时。
表2
从表2中可以看出，钯硫摩尔比低于3时产品芳烃与原料相比已经没有损失，钯硫摩尔比3.5时芳烃稍微有点损失。钯硫摩尔比在这个范围经过运转16小时后，溴指数都可以达到1000以下的要求。也就是说，钯硫摩尔比低于3，就可以达到芳烃损失小于0.5（重）%，溴指数低于100mgBr/100g油的要求。
实施例3
在钯硫摩尔比为3的情况下，分别使用二甲二硫，甲基硫醚，硫化氢，丁基硫醇对钯催化剂进行干法钝化，钝化条件是170℃、常压、催化剂装填量50毫升、氢气流量20升/小时。
效果见表3。
表3
表3表明，使用上面这几种硫化物对钯催化剂进行钝化都可以达到对产品溴指数和芳烃损失的要求。
实施例4
在钯硫摩尔比为3的情况下，使用二甲二硫做钝化剂，在不同钝化温度下进行钝化，钝化条件是170℃、常压、催化剂装填量50毫升、氢气流量20升/小时。
然后控制在170℃、1.6MPa、4h-1、氢/油(V)200下加氢反应的结果。
表4
表4加氢反应结果表明，在表中这些温度范围内都可以达到钝化效果。

Claims (1)

1.一种重整生成油选择性加氢的方法，重整生成油，溴指数为7270mgBr/100g油，芳烃重量66.83%，反应条件:170℃、1.6MPa、4h-1、氢/油(V)200；其特征在于：使用的催化剂是含0.3%重量钯的Pd/γ-Al2O3，催化剂在装填前经含硫化合物二甲二硫、甲基硫醚、丁基硫醇或硫化氢干法钝化；硫化物钝化的加入量为钯硫摩尔比1-3.5；钝化温度为常温～230℃。
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CN1210131A (zh) * 1997-10-24 1999-03-10 中国科学院山西煤炭化学研究所 一种重整生成油加氢精制工艺
CN1362493A (zh) * 2001-01-05 2002-08-07 中国石油化工股份有限公司 一种重质油加氢处理催化剂的硫化方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1210131A (zh) * 1997-10-24 1999-03-10 中国科学院山西煤炭化学研究所 一种重整生成油加氢精制工艺
CN1362493A (zh) * 2001-01-05 2002-08-07 中国石油化工股份有限公司 一种重质油加氢处理催化剂的硫化方法

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