CN101104576A - 一种有机含氧化合物和烃类的联合催化转化方法 - Google Patents
一种有机含氧化合物和烃类的联合催化转化方法 Download PDFInfo
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- CN101104576A CN101104576A CNA2006100910746A CN200610091074A CN101104576A CN 101104576 A CN101104576 A CN 101104576A CN A2006100910746 A CNA2006100910746 A CN A2006100910746A CN 200610091074 A CN200610091074 A CN 200610091074A CN 101104576 A CN101104576 A CN 101104576A
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- catalyst
- zeolite
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- bed
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Abstract
一种有机含氧化合物和烃类的联合催化转化方法,有机含氧化合物原料与含Y系列沸石的催化剂接触,反应物流经分离得到积碳催化剂和产物;烃类原料与含Y系列沸石的催化剂接触,反应物流经分离得到待生催化剂和反应油气,油气进一步分离得到气体、汽油等产品;积碳催化剂部分或全部、待生催化剂全部或部分进入再生器进行烧焦再生,再生催化剂分为两部分,其中一部分返回与烃类原料接触,另一部分冷却后返回与有机含氧化合物原料接触。该方法既合理使用了烃类催化转化的过剩热能,又解决了有机含氧化合物转化的供热问题,保证有机含氧化合物连续地催化转化。
Description
技术领域
本发明涉及一种联合有机含氧化合物的催化转化和烃类的催化转化的工艺方法。
背景技术
人类刚刚进入21世纪,全球石油的供需矛盾日益突出。随着各种石油石化产品需求量的增加,市场上原油价格持续走高。这种形势导致了以石油石化产品为原料的重要化工产品低碳烯烃(特别是乙烯、丙烯)、低分子醚(如二甲醚、乙醚等)的市场价格高居不下。因此,寻找其它替代原料如农林副产乙醇、由天然气或煤制得的甲醇生产低碳烯烃、低分子醚成为解决问题的一种选择。
从乙醇制备乙烯的方法是在合适的催化剂作用下,在140~400℃温度范围内发生脱水反应:CH3CH2OH→CH2=CH2+H2O。上世纪80年代初,印度和巴西建立了工业规模乙醇转化生产乙烯的装置,以硅-铝为催化剂,先后采用了固定床、流化床反应器形式。为了维持热平衡,在催化剂再生时要附加一部分燃料。
US6,441,261公开的方法是在在较高压力下,在磷铝硅分子筛催化剂上将含氧化合物(甲醇等)转化成低碳烯烃乙烯和丙烯。
US6,303,839和US5,914,433将含氧化合物(甲醇等)转化成低碳烯烃,将其中的丙烯和/或丁烯分馏出来进行裂化,从而提高乙烯和丙烯的产率。虽然上述方法也采用流化床操作,但是从其实施例数据来看,焦炭产率仅2%。焦炭产率低,系统热平衡难以维系,一般需要外部热量供应。
US6,049,017通过将含有碳4组分的产物分离并在非分子筛催化剂上转化成乙烯和丙烯的方法来增产低碳烯烃,该方法可用于催化裂化或甲醇脱水生产乙烯和丙烯工艺过程。
US4,148,835采用择型及其改性分子筛催化剂将醇类(特别是甲醇)转化成主要含低碳烯烃的产物,该专利没有提及工艺方法。
从甲醇制备二甲醚(DME)的常规方法是,在酸性催化剂作用下甲醇气相脱水生成DME,同时还可生成CO、CO2、CH4、C2H4、H2等副产物。所述酸性催化剂,包括沸石、活性氧化铝、结晶硅酸铝、二氧化硅/氧化铝、阴离子交换树脂等。
醇的脱水反应需要在一定温度下完成。反应过程中虽然有结焦现象,但焦炭量不足以维持工艺过程的热量平衡。综上所述,现有技术均采用外供燃料的方式提供热量,使得工艺过于复杂或能耗过高。
发明内容
本发明的目的是在现有技术的基础上提供一种有机含氧化合物和烃类的联合催化转化方法。
本发明提供的有机含氧化合物和烃类的联合催化转化方法包括下列步骤:
(1)、有机含氧化合物原料与含Y系列沸石的催化剂接触,反应物流经分离得到积炭催化剂和产物;
(2)、烃类原料与含Y系列沸石的催化剂接触,反应物流经分离得到待生催化剂和反应油气,油气进一步分离得到气体、汽油等产品;
(3)、步骤(1)的积炭催化剂部分或全部、步骤(2)的待生催化剂全部或部分进入再生器进行烧焦再生,再生催化剂分为两部分,其中一部分返回步骤(2),另一部分冷却后返回步骤(1)。
本发明所述有机含氧化合物原料中有机含氧化合物的含量为10-100重%优选50-100重%更优选90-100重%,可以含有少量杂质。所述有机含氧化合物选自醇类、醚类、酮类、羧酸、环醚、醛类、多羟基化合物中的一种或一种以上的混合物,优选的有机含氧化合物选自醇类、醚类化合物中的一种或一种以上的混合物。
其中所述醇类的碳数为1~10,优选1~5,更优选1~2即甲醇或/和乙醇,羟基数为1~3,优选的羟基数为1即一元醇。醇选自上述碳数、羟基数范围的醇中的一种或一种以上的混合物。所述醇类原料来自各种农林作物经发酵制得的醇,或/和各种化石燃料如天然气、煤、油砂、石油等经气化、合成制得的醇。
所述醚类的碳数最好为2~6,酮类的碳数最好为3~5,羧酸的碳数最好为2~4,环醚的碳数最好为4~6,醛类的碳数最好为1~5;多羟基化合物主要指碳水化合物,为多羟基醛或多羟基酮,包括单糖(如葡萄糖)、低聚糖(如蔗糖)、多糖(如纤维素)等,其碳数最好为3~6。
所述烃类原料选自C4+烃类、原油、汽油、柴油、减压瓦斯油、焦化瓦斯油、脱沥青油、加氢尾油、常压渣油、减压渣油中的一种或一种以上的混合物,优选减压瓦斯油、焦化瓦斯油、脱沥青油、加氢尾油、常压渣油、减压渣油中的一种或一种以上的混合物。
所述含Y系列沸石的催化剂可以是不含无机氧化物和粘土的Y系列沸石和任选的其它分子筛,其中其它分子筛与Y系列沸石的重量比为0-10;优选含无机氧化物、粘土、Y系列沸石、任选的其它分子筛,其中其它分子筛与Y系列沸石的重量比为0-10,其它分子筛与Y系列沸石之和占催化剂总重量的10-60重%。
其中Y系列沸石包括Y型及其衍生或改性沸石,选自Y、HY、REY、REHY、USY、REUSY中的一种或一种以上的混合物。
所述其它分子筛选自中孔沸石、Beta沸石、SAPO分子筛中的一种或几种。
中孔沸石包括ZRP系列(稀土改性)、ZSP系列(铁改性)、ZSM系列沸石及其衍生或改性沸石,有关ZRP更为详尽的描述参见US5,232,675,ZSM系列沸石选自ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、ZSM-35、ZSM-38、ZSM-48和其它类似结构的沸石之中的一种或一种以上的混合物,有关ZSM-5更为详尽的描述参见US3,702,886。
更优选的催化剂含Y系列沸石、中孔沸石、无机氧化物和粘土,其中中孔沸石与Y系列沸石的重量比为0.1-10,中孔沸石与Y系列沸石之和占催化剂总重量的10-60重%。
所述无机氧化物选自氧化铝、氧化硅、无定型硅铝中的一种或一种以上的混合物,粘土为高岭土或/和多水高岭土。
步骤(1)的反应条件如下:温度50~500℃,压力(表压)0~0.8MPa,催化剂与有机含氧化合物原料的重量比为0.001~50,重时空速0.05~10h-1优选0.1~8h-1。
步骤(2)的反应条件如下:温度400~700℃,压力(表压)0~0.8MPa,催化剂与烃类原料的重量比为1~30,时间1~10s。
步骤(2)的催化转化工艺包括常规催化裂化工艺及其各种家族工艺技术如DCC工艺、CPP工艺、MIP工艺、MIP-CGP工艺、MGD工艺、MGG工艺、ARGG工艺、SHMP工艺等。
步骤(1)的积炭催化剂中参与烧焦的部分占积炭催化剂总重量的0.5-100%。当步骤(1)的部分积炭催化剂进入再生器进行烧焦再生的情况下,剩余的积炭催化剂返回步骤(1)或/和步骤(2),所述部分积炭催化剂占积炭催化剂总重量的0.5-99%。
步骤(2)的待生催化剂中参与烧焦的部分占待生催化剂总重量的1-100%。当步骤(2)的部分待生催化剂进入再生器进行烧焦再生的情况下,剩余的待生催化剂返回步骤(1),所述部分待生催化剂占待生催化剂总重量的1-99%。
步骤(3)所述再生为单段再生或两段再生,所述再生催化剂为部分再生催化剂(即半再生催化剂)或/和完全再生催化剂。
步骤(1)、步骤(2)所用的反应器均为催化剂可移动的反应器,选自流化床、提升管、下行式输送线反应器、移动床、由提升管与流化床构成的复合反应器、由提升管与下行式输送线构成的复合反应器、由两个或两个以上的提升管构成的复合反应器、由两个或两个以上的流化床构成的复合反应器、由两个或两个以上的下行式输送线构成的复合反应器、由两个或两个以上的移动床构成的复合反应器,上述每种反应器可以分成两个或两个以上的反应区。步骤(1)优选的反应器为流化床更优选密相流化床;步骤(2)优选的反应器为提升管。所述提升管选自等直径提升管、等线速提升管、各种变直径提升管中的一种或几种。所述流化床选自固定流化床、散式流化床、鼓泡床、湍动床、快速床、输送床、密相流化床中的一种或几种。
上述反应器可以使用现有的催化裂化反应器,也可以对现有的催化裂化反应器进行必要的改造,还可以使用与现有催化裂化反应器结构和功能类似的反应器。
步骤(1)、步骤(2)所用的产品分离装置可以共用同一个,也可分别用不同的。步骤(1)分离的过剩有机含氧化合物可以返回步骤(1),步骤(2)分离的C4+低碳烃可以返回步骤(1)或/和步骤(2)。
返回步骤(1)反应器的再生催化剂先经冷却至50-650℃。可采用直接或间接换热方式冷却。直接换热方式就是用温度较低的空气与再生催化剂直接接触换热。这股空气是经空压机压缩被送往再生器空气的全部或一部分,即利用部分再生剂的高温热能预热进入再生器的空气。直接换热器形式为流化床或提升管,经旋风分离器分离的被冷却的催化剂经过热水蒸汽汽提杂质气体(氮、氧、二氧化碳等)后进有机含氧化合物催化转化反应器;间接换热方式就是用间接换热器,热的催化剂从管程通过,水蒸汽走壳程。
采用本发明提出的联合催化转化有机含氧化合物和烃类的方法,既合理使用了烃类催化转化的过剩热能,又解决了有机含氧化合物转化的供热问题,保证有机含氧化合物连续地催化转化。
附图说明
附图为本发明提供的有机含氧化合物和烃类的联合催化转化方法原则流程示意图。
具体实施方式
下面结合附图对本发明所提供的方法进行进一步的说明,但并不因此限制本发明。
附图为本发明提供的有机含氧化合物和烃类的联合催化转化方法原则流程示意图。
来自管线1的有机含氧化合物原料进入反应器2,与来自管线14的含Y系列沸石的催化剂接触,在温度50~500℃,压力(表压)0~0.8MPa,催化剂与有机含氧化合物原料的重量比为0.001~50,重时空速0.1~10h-1的条件下反应,反应物流经分离得到积炭催化剂和产物流,该产物流经管线3引出进一步分离得到产物,过剩的有机含氧化合物原料循环使用(图中未标出),积炭催化剂则可以部分或全部经管线4去再生器5进行烧焦再生,部分积炭催化剂可以依次经管线15、14返回反应器2,也可以依次经管线17、10返回反应器7。
来自管线6的烃类原料进入反应器7,与来自管线10的含Y系列沸石的再生催化剂接触,在温度400~700℃,压力(表压)0~0.8MPa,催化剂与烃类原料的重量比为1~30,时间1~10s的条件下反应,反应物流经分离得到待生催化剂和反应油气,其中反应油气经管线8引出进一步分离得到气体、汽油、柴油等产品(图中未标出),待生催化剂汽提后,全部或部分经管线9进入再生器5进行烧焦再生,部分待生催化剂可以依次经管线16、14返回反应器2。
在再生器5烧焦再生后的再生催化剂分为两部分,其中一部分经管线10返回反应器7,另一部分依次经管线12进入换热器13冷却后,再经管线14返回反应器2。
下面的实施例将对本方法予以进一步的说明,但并不因此限制本方法。
实施例1
本实施例中所用的有机含氧化合物原料、烃类原料分别为由粮食酿造的含95%乙醇的乙醇原料、减压瓦斯油(VGO),VGO的性质如表1所示。本实施例中所用的催化剂牌号为CGP-1(含25重%REY沸石,10重%ZSP沸石,余量为载体,均以催化剂总重量为基准),由中国石化股份有限公司催化剂齐鲁分公司生产。
乙醇原料进入流化床反徉器与CGP-1催化剂接触,在温度340℃,压力(表压)0.1MPa,催化剂与乙醇原料的重量比(剂醇比)为1,重时空速1.0h-1的条件下反应,反应物流经分离得到积炭催化剂和产物流,该产物流进一步分离得到目的产物乙烯,产品分布如表2所示;积炭催化剂分为两部分,其中20重%的积炭催化剂去再生器进行烧焦再生,剩余80重%的积炭催化剂内循环返回流化床反应器。
预热后的VGO经蒸汽雾化后注入提升管反应器中,蒸汽与VGO的重量比为0.1∶1,VGO在提升管内与热的CGP-1催化剂接触并反应,反应温度为500℃,压力(表压)0.1MPa,催化剂与VGO的重量比(剂油比)为6,反应时间为3秒,反应油气和催化剂的混合物沿提升管上行至提升管出口处后,分离反应产物和待生催化剂,反应产物引入沉降器后再引入后续分离系统中,进一步分离为各种产品,产品分布如表2所示;而待生催化剂在重力的作用下进入汽提器,经水蒸汽汽提后送入再生器中烧焦再生。
20重%的积炭催化剂和全部的待生催化剂再生后,分为两部分,其中85重%的680℃再生催化剂返回提升管循环使用,剩余的15重%的再生催化剂冷却至410℃返回流化床循环使用。
试验结果显示,乙醇的催化转化与烃类的催化转化联合后,能维持二者的热平衡,不需要外加燃料或其它热源。
实施例2
本实施例中所用的有机含氧化合物原料、烃类原料分别为甲醇(化学纯,河北新乐化工厂生产)、VGO掺30重%的常压渣油,常压渣油的性质如表1所示。本实施例中所用的催化剂牌号为CGP-2(含30重%USY沸石,5重%ZSP沸石,余量为载体,均以催化剂总重量为基准),由中国石化股份有限公司催化剂齐鲁分公司生产。
液态甲醇原料进入流化床反应器与CGP-2催化剂接触,在温度250℃,压力(表压)0.1MPa,催化剂与甲醇原料的重量比(剂醇比)为6,重时空速3h-1的条件下反应,反应物流经分离得到积炭催化剂和产物流,该产物流进一步分离得到目的产物二甲醚,产品分布如表3所示,过量的甲醇返回流化床反应器;积炭催化剂分为两部分,其中50重%的积炭催化剂去再生器进行烧焦再生,剩余50重%的积炭催化剂内循环返回流化床反应器。
预热后的VGO与常压渣油的混合原料油经蒸汽雾化后注入提升管反应器中,蒸汽与混合原料油的重量比为0.05∶1,混合原料油在提升管内与热的再生催化剂接触并反应,反应温度为500℃,压力(表压)0.1MPa,催化剂与混合原料油的重量比(剂油比)为6,反应时间为3秒,反应油气和催化剂的混合物沿提升管上行至提升管出口处后,分离反应产物和待生催化剂,反应产物引入沉降器后再引入后续分离系统中,进一步分离为各种产品,产品分布如表3所示;而待生催化剂在重力的作用下进入汽提器,经水蒸汽汽提后送入再生器中烧焦再生。
50重%的积炭催化剂和全部的待生催化剂再生后,分为两部分,其中90重%的690℃再生催化剂返回提升管循环使用,剩余的10重%的再生催化剂冷却至540℃返回流化床循环使用。
试验结果显示,甲醇的催化转化与烃类的催化转化联合后,能维持二者的热平衡,不需要外加燃料或其它热源。
实施例3
与实施例1中原料为乙醇的工艺相同,将原料换成乙醚,反应结果如表4所示。
实施例4-6
与实施例1中原料为乙醇的工艺相同,将原料分别换为丙醇、丁醇、丙三醇,醇的反应结果如表5所示。
实施例7
本实施例中所用的有机含氧化合物原料、烃类原料分别为甲醇(化学纯,河北新乐化工厂生产)、VGO掺30重%的常压渣油,常压渣油的性质如表1所示。本实施例中所用的催化剂牌号为MPO51(含5重%USY沸石,30重%ZSP沸石,余量为载体,均以催化剂总重量为基准),由中国石化股份有限公司催化剂齐鲁分公司生产。
甲醇原料进入流化床反应器与MPO51催化剂接触,在温度550℃,压力(表压)0.1MPa,催化剂与甲醇原料的重量比(剂醇比)为2,重时空速1.2h-1的条件下反应,反应物流经分离得到积炭催化剂和产物流,该产物流进一步分离得到目的产物丙烯,产品分布如表6所示,过量的甲醇返回流化床反应器;积炭催化剂分为两部分,其中50重%的积炭催化剂去再生器进行烧焦再生,剩余50重%的积炭催化剂内循环返回流化床反应器。
预热后的VGO与常压渣油的混合原料油经蒸汽雾化后注入提升管反应器中,蒸汽与混合原料油的重量比为0.05∶1,混合原料油在提升管内与热的再生催化剂接触并反应,反应温度为500℃,压力(表压)0.1MPa,催化剂与混合原料油的重量比(剂油比)为6,反应时间为3秒,反应油气和催化剂的混合物沿提升管上行至提升管出口处后,分离反应产物和待生催化剂,反应产物引入沉降器后再引入后续分离系统中,进一步分离为各种产品,产品分布如表6所示;而待生催化剂在重力的作用下进入汽提器,经水蒸汽汽提后送入再生器中烧焦再生。
50重%的积炭催化剂和全部的待生催化剂再生后,分为两部分,其中90重%的690℃再生催化剂返回提升管循环使用,剩余的10重%的再生催化剂冷却至600℃返回流化床循环使用。
试验结果显示,甲醇的催化转化与烃类的催化转化联合后,能维持二者的热平衡,不需要外加燃料或其它热源。
实施例8-9
与实施例1的工艺相同,将原料分别换为含乙醇15%、50%的乙醇水溶液,目的产物为乙醚,反应结果如表7所示。
表1
原料性质 | VGO | 常压渣油 |
密度(20℃),g/cm3 | 0.9071 | 0.9387 |
硫含量,ppm | 7800 | 12000 |
氮含量,ppm | 600 | 647 |
残炭,m% | 0.1 | 9.2 |
C,m% | 86.43 | 87.05 |
H,m% | 12.48 | 11.83 |
运动粘度,mm2/s | ||
80℃ | 21.28 | 325.1 |
100℃ | 11.32 | 129.5 |
凝点,℃ | 35 | 45 |
实沸点,℃ | >350 | >450 |
钒,ppm | 0.3 | 1.7 |
镍,ppm | 4.2 | 30 |
表2
实施例1 | 原料为乙醇 |
有机含氧化合物的催化转化 | |
反应条件 | |
温度,℃ | 340 |
压力(表压),MPa | 0.1 |
剂醇比 | 1 |
重时空速,h-1 | 1.0 |
产品分布,体% | |
乙烯 | 95.79 |
丙烯 | 1.18 |
总C4烃 | 0.72 |
总C5烃 | 0.70 |
C6以上烃 | 0.54 |
乙醇的转化率,% | 99.1 |
乙烯选择性,% | 95.2 |
碳基乙烯产率*,m% | 89.52 |
烃类的催化转化 | |
反应条件 | |
温度,℃ | 550 |
压力(表压),MPa | 0.1 |
剂油比 | 6 |
时间,s | 3 |
产品分布,重% | |
干气 | 10.56 |
液化气 | 44.78 |
汽油 | 21.32 |
柴油 | 4.89 |
重油 | 3.18 |
焦炭 | 15.28 |
表3
实施例2 | 原料为甲醇 |
有机含氧化合物的催化转化 | |
反应条件 | |
温度,℃ | 250 |
压力(表压),MPa | 0.1 |
剂醇比 | 6 |
重时空速,h-1 | 3.0 |
产品分布,m% | |
二甲醚 | 53.11 |
轻质烃类 | 0.90 |
水 | 25.41 |
焦炭 | 1.12 |
未转化甲醇 | 19.46 |
甲醇的转化率,% | 80.54 |
二甲醚选择性,% | >98 |
烃类的催化转化 | |
反应条件 | |
温度,℃ | 500 |
压力(表压),MPa | 0.1 |
剂油比 | 6 |
时间,s | 3 |
产品分布,重% | |
干气 | 3.17 |
液化气 | 18.04 |
汽油 | 48.26 |
柴油 | 18.73 |
重油 | 4.56 |
焦炭 | 7.24 |
表4
实施例3 | 原料为乙醚 |
有机含氧化合物的催化转化 | |
反应条件 | |
温度,℃ | 360 |
压力(表压),MPa | 0.1 |
剂醇比 | 10 |
重时空速,h-1 | 1.0 |
产品分布,体% | |
乙烯 | 83.57 |
C+ 3 | 13.52 |
焦炭 | 2.72 |
液体 | 0.19 |
烃类的催化转化 | |
反应条件 | |
温度,℃ | 550 |
压力(表压),MPa | 0.1 |
剂油比 | 6 |
时间,s | 3 |
产品分布,重% | |
干气 | 10.56 |
液化气 | 44.78 |
汽油 | 21.32 |
柴油 | 4.89 |
重油 | 3.18 |
焦炭 | 15.28 |
表5
实施例 | 4 | 5 | 6 |
原料 | 丙醇 | 丁醇 | 丙三醇 |
有机含氧化合物的催化转化 | |||
反应条件 | |||
温度,℃ | 150 | 480 | 60 |
压力(表压),MPa | 0.1 | 0.1 | 0.1 |
剂醇比 | 25 | 45 | 0.005 |
重时空速,h-1 | 5 | 10 | 0.1 |
原料的转化率,% | 90 | 87 | 96 |
目的产物的选择性,% | 丙烯/92 | C4烯/95 | 丙烯醛/71 |
表6
实施例7 | 原料为甲醇 |
有机含氧化合物的催化转化 | |
反应条件 | |
温度,℃ | 550 |
压力(表压),MPa | 0.1 |
剂醇比 | 2 |
重时空速,h-1 | 1.2 |
产品分布,m% | |
乙烯* | 6.62 |
丙烯* | 42.79 |
其它轻质烃类* | 39.44 |
水 | 57.36 |
焦炭 | 1.12 |
未转化甲醇 | 0.46 |
甲醇的转化率,% | 99.89 |
丙烯选择性*,% | >30 |
烃类的催化转化 | |
反应条件 | |
温度,℃ | 500 |
压力(表压),MPa | 0.1 |
剂油比 | 6 |
时间,s | 3 |
产品分布,重% | |
干气 | 3.17 |
液化气 | 18.04 |
汽油 | 48.26 |
柴油 | 18.73 |
重油 | 4.56 |
焦炭 | 7.24 |
*以烃类产品的总量为基准,水不包括在内
表7
实施例 | 8 | 9 |
原料 | 乙醇15% | 乙醇50% |
有机含氧化合物的催化转化 | ||
反应条件 | ||
温度,℃ | 150 | 200 |
压力(表压),MPa | 0.1 | 0.1 |
剂醇比 | 20 | 5 |
重时空速,h-1 | 6 | 9 |
原料的转化率,% | 70 | 88 |
产品分布,体% | ||
乙烯 | 9.0 | 15.3 |
乙醚 | 89.88 | 83.51 |
丙烯 | 0.18 | 0.23 |
总C4烃 | 0.53 | 0.35 |
总C5烃 | 0.09 | 0.20 |
C6以上烃 | 0.32 | 0.41 |
Claims (32)
1.一种有机含氧化合物和烃类的联合催化转化方法,其特征在于该方法包括下列步骤:
(1)、有机含氧化合物原料与含Y系列沸石的催化剂接触,反应物流经分离得到积炭催化剂和产物;
(2)、烃类原料与含Y系列沸石的催化剂接触,反应物流经分离得到待生催化剂和反应油气,油气进一步分离;
(3)、步骤(1)的积炭催化剂部分或全部、步骤(2)的待生催化剂全部或部分进入再生器进行烧焦再生,再生催化剂分为两部分,其中一部分返回步骤(2),另一部分冷却后返回步骤(1)。
2.按照权利要求1的方法,其特征在于所述有机含氧化合物原料中有机含氧化合物的含量为10-100重%。
3.按照权利要求1或2的方法,其特征在于所述有机含氧化合物选自醇类、醚类、酮类、羧酸、环醚、醛类、多羟基化合物中的一种或一种以上的混合物。
4.按照权利要求1或2的方法,其特征在于所述有机含氧化合物选自醇类、醚类化合物中的一种或一种以上的混合物。
5.按照权利要求3的方法,其特征在于所述醇的碳数为1~10,羟基数为1~3。
6.按照权利要求3的方法,其特征在于所述醇的碳数为1~5,羟基数为1。
7.按照权利要求3的方法,其特征在于所述醚类的碳数为2~6。
8.按照权利要求3的方法,其特征在于所述酮类的碳数为3~5,羧酸的碳数为2~4,环醚的碳数为4~6,醛类的碳数为1~5。
9.按照权利要求3的方法,其特征在于所述多羟基化合物为多羟基醛或多羟基酮,其碳数为3~6。
10.按照权利要求1的方法,其特征在于所述烃类原料选自C4+烃类、原油、汽油、柴油、减压瓦斯油、焦化瓦斯油、脱沥青油、加氢尾油、常压渣油、减压渣油中的一种或一种以上的混合物。
11.按照权利要求1的方法,其特征在于所述烃类原料选自减压瓦斯油、焦化瓦斯油、脱沥青油、加氢尾油、常压渣油、减压渣油中的一种或一种以上的混合物。
12.按照权利要求1的方法,其特征在于所述含Y系列沸石的催化剂是不合无机氧化物和粘土的Y系列沸石和任选的其它分子筛。
13.按照权利要求1的方法,其特征在于所述含Y系列沸石的催化剂包括合无机氧化物、粘土、Y系列沸石和任选的其它分子筛。
14.按照权利要求12或13的方法,其特征在于所述其它分子筛选自中孔沸石、Beta沸石、SAPO分子筛中的一种或几种。
15.按照权利要求12或13的方法,其特征在于所述其它分子筛与Y系列沸石的重量比为0-10。
16.按照权利要求1的方法,其特征在于所述含Y系列沸石的催化剂包括Y系列沸石、中孔沸石、无机氧化物和粘土。
17.按照权利要求1、12或13的方法,其特征在于所述Y系列沸石选自Y、HY、REY、REHY、USY、REUSY中的一种或一种以上的混合物。
18.按照权利要求14或16的方法,其特征在于所述中孔沸石包括ZRP系列、ZSP系列、ZSM系列沸石及其衍生或改性沸石。
19.按照权利要求16的方法,其特征在于所述中孔沸石与Y系列分子筛的重量比为0.1-10,中孔沸石与Y系列沸石之和占催化剂总重量的10-60重%。
20.按照权利要求12或13的方法,其特征在于所述无机氧化物选自氧化铝、氧化硅、无定型硅铝中的一种或一种以上的混合物,粘土为高岭土或/和多水高岭土。
21.按照权利要求1的方法,其特征在于步骤(1)的反应条件为:温度50~500℃,压力0~0.8MPa,催化剂与有机含氧化合物原料的重量比为0.001~50,重时空速0.05~10h-1。
22.按照权利要求1的方法,其特征在于步骤(2)的反应条件为:温度400~700℃,压力0~0.8MPa,催化剂与烃类原料的重量比为1~30,时间1~10s。
23.按照权利要求1的方法,其特征在于步骤(1)的积炭催化剂中参与烧焦的部分占积炭催化剂总重量的0.5-100%。
24.按照权利要求1或23的方法,其特征在于当步骤(1)的部分积炭催化剂进入再生器进行烧焦再生的情况下,剩余的积炭催化剂返回步骤(1)或/和步骤(2),所述部分积炭催化剂占积炭催化剂总重量的0.5-99%。
25.按照权利要求1的方法,其特征在于步骤(2)的待生催化剂中参与烧焦的部分占待生催化剂总重量的1-100%。
26.按照权利要求1或25的方法,其特征在于当步骤(2)的部分待生催化剂进入再生器进行烧焦再生的情况下,剩余的待生催化剂返回步骤(1),所述部分待生催化剂占待生催化剂总重量的1-99%。
27.按照权利要求1的方法,其特征在于步骤(3)所述再生为单段再生或两段再生,所述再生催化剂为部分再生催化剂或/和完全再生催化剂。
28.按照权利要求1的方法,其特征在于步骤(1)、步骤(2)所用的反应器均为催化剂可移动的反应器,选自流化床、提升管、下行式输送线反应器、移动床、由提升管与流化床构成的复合反应器、由提升管与下行式输送线构成的复合反应器、由两个或两个以上的提升管构成的复合反应器、由两个或两个以上的流化床构成的复合反应器、由两个或两个以上的下行式输送线构成的复合反应器、由两个或两个以上的移动床构成的复合反应器,上述每种反应器可以分成两个或两个以上的反应区。
29.按照权利要求1的方法,其特征在于步骤(1)的反应器为流化床;步骤(2)的反应器为提升管。
30.按照权利要求28或29的方法,其特征在于所述提升管选自等直径提升管、等线速提升管、各种变直径提升管中的一种或几种;所述流化床选自固定流化床、散式流化床、鼓泡床、湍动床、快速床、输送床、密相流化床中的一种或几种。
31.按照权利要求1的方法,其特征在于返回步骤(1)反应器的再生催化剂先采用直接或间接的换热方式冷却至50-650℃。
32.按照权利要求28的方法,其特征在于所述直接换热方式是用温度较低的空气与再生催化剂直接接触换热,直接换热器形式为流化床或提升管;间接换热方式是用间接换热器,热的催化剂从管程通过,水蒸汽走壳程。
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US8373013B2 (en) | 2013-02-12 |
ZA200900119B (en) | 2010-05-26 |
EP2042476A4 (en) | 2011-08-31 |
US20090318742A1 (en) | 2009-12-24 |
EP2042476B1 (en) | 2018-01-10 |
CA2656861A1 (en) | 2008-01-24 |
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