CN112410064A - 一种焦化汽油加氢脱二烯烃的方法 - Google Patents
一种焦化汽油加氢脱二烯烃的方法 Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 67
- 239000003502 gasoline Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004939 coking Methods 0.000 title claims abstract description 37
- 150000001993 dienes Chemical class 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 239000011733 molybdenum Substances 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 150000001336 alkenes Chemical group 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
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- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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Abstract
本发明公开了一种焦化汽油加氢脱二烯烃的方法,该方法将焦化汽油原料在管线中进行氢气饱和,然后进入一个或多个反应换热器装置,原料油由装置换热管程一端进入,进行物料换热的同时流经换热管程内的整体式加氢催化剂,发生加氢脱二烯烃反应,加氢产物从换热管程另一端流出,去后续的加氢精制反应器进行加工处理。本发明方法可避免换热器或催化剂床层结焦,降低后续加氢反应器压差;并且本发明方法无需对现有装置进行大的改动,能够在较小的投资下,实现装置的长周期运转,提升装置经济效益。
Description
技术领域
本发明属于石油与天然气加工领域,涉及一种焦化汽油加氢脱二烯烃的方法。
背景技术
延迟焦化是一种重要的石油二次加工技术,也是世界渣油深度加工的主要方法之一,其处理能力约占全球渣油处理能力的三分之一。延迟焦化的主要产品包括气体、汽油、柴油、蜡油和焦炭,其中的汽柴油混合加氢精制后可用于生产国V柴油和重整原料。焦化产品之一焦化汽油中烯烃、硫、氮、硅等杂原子含量高,安定性差,不能直接作为产品使用,甚至不能直接作为下游装置的进料。为使焦化汽油满足终端产品标准或符合下游装置的进料要求,必须进行加氢精制或加氢处理。
在焦化汽油中,二烯烃、烯基芳烃及炔烃等化合物含量较高,且这些不饱和化合物极不稳定,尤其是二烯烃,受热后易发生环化反应和聚合反应形成大分子化合物,并与汽油中的细小焦粉粘结、长大,造成炼厂后续加氢精制工段中催化剂床层易结焦,加氢反应器压差增大。
焦化汽油加氢反应器压降的上升均来自于催化剂上部床层结焦。经大量研究表明,结焦因素很复杂,但是主要由于原料中的二烯烃等不饱和烃类的聚合以及上游装置带入的机械杂质沉积在催化剂床层上部导致。原料中的二烯烃在低温条件下就能够发生聚合,先生成低聚物,随后迅速向高聚物转化直至结焦。二烯烃含量高时在加氢精制工段换热器中就发生结焦,严重影响生产效率;同时造成换热器清洗次数增加,清洗困难。为此,有必要针对性的在加氢精制工段前增设焦化汽油脱二烯烃装置,提高生产稳定性。
中国专利CN101164691A公开了一种轻汽油选择性加氢脱二烯烃催化剂及其制备方法,其采用一种特殊的金属氧化铈复合氧化物,用于C3~C6馏分轻汽油的加氢精制,在反应温度40~70℃,氢分压力1.0~3.0MPa,空速0.5~4.0h-1,氢油体积比100~700工艺条件下,原料中二烯烃的脱除率大于97%。
中国专利103084193A公开了一种裂解汽油和催化汽油选择性加氢脱二烯烃催化剂及制备方法,其选用ZrO2~Al2O3作为载体负载活性金属,在反应温度100~240℃,氢分压力1.0~5.0MPa,空速3.0~12.0h-1,氢油体积比50~500工艺条件下,原料中二烯烃的脱除率达到75~98%;
中国专利1676580A公开了一种馏分油选择性加氢脱二烯烃的方法,其采用多金属负载型催化剂,在反应温度160~300℃,氢分压力1.0~6.0MPa,空速2.0~30.0h-1,氢油体积比50~600工艺条件下,原料中二烯烃的脱除率大于88%。
中国专利CN 107955642 A公开了一种碳五抽余油及焦化汽油混合加氢的方法和碳五抽余油及焦化汽油混合加氢的系统。所述碳五抽余油及焦化汽油混合加氢的方法包括:将碳五抽余油进行预加氢反应,使得该碳五抽余油中的二烯烃加氢饱和,将所述预加氢反应所得产物作为稀释剂与焦化汽油共同进行加氢反应。
上述专利选用的工艺都为常规气相循环滴流床加氢工艺。均需要在现有加氢装置前增设一个反应器,原料油经换热后与氢气混合进入加氢脱二烯烃反应器,增大了企业的成本投入。当原料油中二烯烃含量高时发生换热器内或者在加氢反应器结焦,导致换热器堵塞或加氢反应器压降增加,引起装置停工。
发明内容
为克服现有技术不足,本发明提供了一种焦化汽油加氢脱二烯烃的方法。本发明方法无需对现有装置进行大的改动,能够在较小的投资下,实现装置的长周期运转,提升装置经济效益。
本发明焦化汽油加氢脱二烯烃方法具体内容包括:将焦化汽油原料在管线中进行氢气饱和,饱和溶解氢的混合物进入反应换热器装置,原料油由装置换热管程一端进入,进行物料换热的同时流经换热管程内的整体式加氢催化剂,发生加氢脱二烯烃反应,加氢产物从换热管程另一端流出,去后续的加氢精制反应器进行加工处理;所述的换热管程内加氢反应条件为:反应温度为90~200℃,优选为100~180℃,反应压力为1.2~8.0MPa,优选为1.8~6.5MPa。
所述的反应换热器装置结构采用现有常用管壳式换热器结构,换热管程内径一般为16mm、20mm或25mm三种型号。
所述的整体式加氢催化剂结构为蜂窝状柱形,其外径小于换热管程内径1~2mm,利于催化剂装填进入换热管程内,换热管程加氢产物流出一端设置结构设计可防止催化剂流出,但不影响物料流动。整体式催化剂在单个换热管程内可以是多根,一般视管程长度而定。
所述的整体式加氢催化剂由金属活性组分和载体组成,其中所述的金属活性组分为MoO3、WO3、NiO、Co2O3中的一种或多种,总活性金属氧化物含量占催化剂质量的8%~22%,优选为12~20%,余量为载体,载体由大孔氧化铝组成,,其形状为蜂窝状柱形,催化剂比表面积为160~260m2/g,孔容为0.3~0.8mL/g。
所述的整体式加氢催化剂制备过程载体采用氧化铝、粘结剂与水混合后,经挤出机挤出、整形成规整蜂窝状柱形,再经干燥、焙烧处理,柱形外径小于换热管程内径1mm,一般为15mm、19mm或24mm三种尺寸,长度在0.3m到1m之间。蜂窝状内部开孔形状可以是圆形或者正方形等,保证物料畅通流动。成型载体采用业内已知的常规浸渍方法负载金属活性组分。
当采用多个反应换热器装置时,可设置为串联方式或并联方式,优选为串联方式。采用多个反应换热器装置并联方式时,控制物料流入反应换热器装置温度不低于90℃,但不高于150℃;采用多个反应换热器装置串联方式时,控制物料流入第一个反应换热器装置温度不低于80℃,但不高于120℃。
本发明的焦化汽油加氢脱二烯烃的方法效果好,不用增设二烯烃加氢反应器,对于现有换热器进行改造或者增设反应换热器装置就能达到二烯烃脱除效果。采用换热器在对原料换热的同时,发生二烯烃加氢饱和放热反应,提高原料温度,可降低后续加热炉负荷,具有节能效果。当焦化汽油与其它物料混合进行加氢精制时,本方法仅针对焦化汽油进行脱二烯烃处理。增设反应换热器装置位置可以在焦化装置汽油分离塔顶部汽油馏出位置,或者是进入后续加氢精制反应器装置与其它加氢原料混合之前位置。换热热源可以是反应装置产物、过热蒸汽或者其它可利用热源。
针对二烯烃含量较高的焦化汽油原料,本方法采用独特的焦化汽油二烯烃脱除技术与整体式加氢催化剂,有效降低了焦化汽油原料中二烯烃在换热器或者加氢精制反应器结焦问题。采用该方法连续运转1000h,产品油颜色由原料的深棕色变为浅黄色,产品二烯值小于0.5gI2/(100g油),二烯烃脱除率大于90%。
本发明方法不仅适用于焦化汽油,也可适用于其它二烯烃含量高的催化裂化汽油和裂解汽油等。
下面的实施例及附图将对本发明方法予以进一步的说明,但并不因此而限制本发明。
附图说明
图1是圆柱形蜂窝状条整体型载体。
图2是圆柱形蜂窝状条整体型载体开孔形状图。
图3是本发明反应换热装置管程中整体式加氢催化剂。
图4为本发明焦化汽油加氢脱二烯烃的方法采用单个反应换热器装置一种优选实施方式的流程示意图。
其中:1是焦化汽油原料,2是新氢,3是原料油泵,4是反应换热器装置,5是脱二烯烃加氢产品物料,7是加热炉,8是焦化汽油加氢精制反应器,9是加氢精制产品,10是换热后去后续分离单元加氢精制产品。
图5为本发明一种焦化汽油加氢脱二烯烃的方法采用两个串联反应换热器装置,然后与焦化柴油混合加氢精制一种优选实施方式的流程示意图。
其中:1是焦化汽油原料,2是新氢,3是原料油泵,4是一级反应换热器装置,5是经一级脱二烯烃加氢产品物料,6是串联二级反应换热器装置,7是加热炉,8是焦化汽柴油加氢精制反应器,9是加氢精制产品,10是换热后去后续分离单元加氢精制产品,11是换热蒸汽或其它热源物料,12是换热后蒸汽或其它热源物料,13是经串联二级脱二烯烃加氢产品物料,14是加氢精制产品与混合原料换热器。
具体实施方式
下面结合实例进一步阐述本发明的技术方案。其中焦化汽油中的二烯烃含量采用UOP326法(又称马来酸酐法)测得。
实施例1
本实例说明本发明提供的整体式加氢催化剂A及其制备方法。
称取山西中海炬华催化材料有限公司生产的干胶粉2000g,挤成外圆直径为15mm的圆柱形蜂窝状条,然后断条至长度为400mm,经整形处理规整,其外形示意如下图1,蜂窝开孔形状见图2中A,120℃烘干,650℃空气气氛下焙烧3小时,得到整体式载体。
控制金属盐溶液浓度,采用等体积浸渍的方法在整体式载体引入镍、钼活性金属。浸渍整体式载体于120℃干燥4小时、450℃焙烧4小时,降至室温,得到整体式加氢催化剂A,其物化性质见表1。
实施例2
本实例说明本发明提供的整体式加氢催化剂B及其制备方法。
称取山西中海炬华催化材料有限公司生产的干胶粉2000g,挤成外圆直径为15mm的圆柱形蜂窝状条,然后断条至长度为300mm,经整形处理规整,蜂窝开孔如图2中B形状,120℃烘干,650℃空气气氛下焙烧3小时,得到整体式载体。
控制金属盐溶液浓度,采用等体积浸渍的方法在整体式载体引入钴、钼活性金属。浸渍整体式载体于120℃干燥4小时、420℃焙烧4小时,降至室温,得到整体式加氢催化剂B,其物化性质见表1。
实施例3
本实例说明本发明提供的整体式加氢催化剂C及其制备方法。
称取山西中海炬华催化材料有限公司生产的干胶粉2000g,挤成外圆直径为15mm的圆柱形蜂窝状条,然后断条至长度为300mm,经整形处理规整,蜂窝开孔如图2中B形状,120℃烘干,650℃空气气氛下焙烧3小时,得到整体式载体。
控制金属盐溶液浓度,采用等体积浸渍的方法在整体式载体引入镍、钨活性金属。浸渍整体式载体于120℃干燥4小时、420℃焙烧4小时,降至室温,得到整体式加氢催化剂C,其物化性质见表1。
表1
实施例5-9
实施例5-9说明本发明提供催化剂用于焦化汽油的二烯烃加氢性能。
实施例5-9选用了3种焦化汽油原料,其性质如表2所示。
表2焦化汽油原料油性质
名称 | 原料油1 | 原料油2 | 原料油3 |
密度(20℃),kg/m<sup>3</sup> | 734.8 | 765.1 | 748.2 |
二烯值,gI<sub>2</sub>/100g油 | 1.95 | 2.37 | 4.66 |
溴价,gBr<sub>2</sub>/100g油 | 53.5 | 48.4 | 41.7 |
胶质含量,mg/100ml油 | 174 | 118 | 194 |
色度(Hazen法) | 25600 | 19700 | 27400 |
以焦化汽油为原料,在实验室反应换热装置上评价整体式加氢催化剂A、B、C及反应换热工艺条件。采用实验室反应换热装置上,选取5根整体式催化剂装入反应换热装置管程中,装填见图3所示,装填完成后两端密封,溶解氢气的焦化汽油由一端进入,从另一端流出。实施例5-8采用一段反应换热装置操作,实施例9采用两段串联反应换热装置操作。整体式加氢催化剂在正式进料前,先用含2重%二硫化碳的直馏汽油对催化剂进行硫化,硫化条件为:氢分压1.6MPa、硫化温度230℃、液时空速2h-1、氢油体积比300、硫化时间8小时。催化剂硫化结束后降温切入焦化汽油原料进行反应,外部热源采用导热油供热方式提供,控制入口温度为80-150℃,氢分压为3.5-5.5MPa,体积空速6-12h-1,溶解氢量占原料的0.05-0.20重%。反应24小时后取样分析,结果列于表3。
表3
表3结果表明,按照本发明提供的焦化汽油加氢脱二烯烃催化剂及加氢处理方法,能够有效降低产品中二烯烃与胶质含量,具有优异的加氢脱二烯烃能力和选择性。
Claims (8)
1.一种焦化汽油加氢脱二烯烃的方法,其特征在于,包括:将焦化汽油原料在管线中进行氢气饱和,饱和溶解氢的混合物进入反应换热器装置,原料油由装置换热管程一端进入,进行物料换热的同时流经换热管程内的整体式加氢催化剂,发生加氢脱二烯烃反应,加氢产物从换热管程另一端流出,去后续的加氢精制反应器进行加工处理;其中换热管程内加氢反应条件为:反应温度为90~200℃,反应压力为1.2~8.0MPa。
2.按照权利要求1所述的方法,其特征在于,换热管程内加氢反应条件为:反应温度为100~180℃,反应压力为1.8~6.5MPa。
3.按照权利要求1所述的方法,其特征在于,所述的反应换热器装置为管壳式换热器结构。
4.按照权利要求1所述的方法,其特征在于,所述的整体式加氢催化剂结构为蜂窝状柱形,其外径小于换热管程内径1~2mm;反应换热器装置换热管程内的整体式加氢催化剂为一根或多根。
5.按照权利要求1所述的方法,其特征在于,所述的整体式加氢催化剂由金属活性组分和载体组成,其中所述的金属活性组分为MoO3、WO3、NiO、Co2O3中的一种或多种,总金属活性组分含量占催化剂质量的8%~22%,余量为载体,载体由大孔氧化铝组成,催化剂比表面积为160~260m2/g,孔容为0.3~0.8mL/g。
6.按照权利要求5所述的方法,其特征在于,所述的整体式加氢催化剂中总金属活性组分含量占催化剂质量的12%~20%。
7.按照权利要求5所述的方法,其特征在于,当采用多个反应换热器装置时,多个反应换热器装置设置为串联方式或并联方式。
8.按照权利要求7所述的方法,其特征在于,采用多个反应换热器装置并联方式时,控制物料流入反应换热器装置温度90℃~150℃;采用多个反应换热器装置串联方式时,控制物料流入第一个反应换热器装置温度在80℃~120℃。
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