CN101300325B - 在重油改质中循环活性浆液催化剂组合物的方法 - Google Patents

在重油改质中循环活性浆液催化剂组合物的方法 Download PDF

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CN101300325B
CN101300325B CN2005800304148A CN200580030414A CN101300325B CN 101300325 B CN101300325 B CN 101300325B CN 2005800304148 A CN2005800304148 A CN 2005800304148A CN 200580030414 A CN200580030414 A CN 200580030414A CN 101300325 B CN101300325 B CN 101300325B
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陈开东
J·沙波特
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Abstract

本发明涉及一种在重油改质的工艺中使用浆液催化剂组合物的方法。浆液催化剂组合物不允许沉降，沉降将可能导致失活。将浆液循环到改质反应器中以重复使用，产物不须为脱除催化剂进一步分离。

Description

在重油改质中循环活性浆液催化剂组合物的方法
发明领域
本发明涉及一种在重油改质中使用浆液催化剂组合物的方法。这些重油的特征在于氢碳比低，而炭渣、沥青质、氮、硫和金属含量高。
发明背景
用于重油改质的浆液催化剂组合物由于颗粒尺寸范围在1-20微米，通常不循环使用。试图循环这些催化剂颗粒的那些方法往往需要多个从最终产品中分离和浓缩催化剂的步骤。使用的步骤在炼油领域是众所周知的。其非限制性地包括下列步骤：溶剂脱沥青、离心、过滤、沉降、蒸馏和干燥。用于这些步骤的其它设备非限制性地包括使用旋液分离器、挤出机和转膜蒸发器。
这些催化剂颗粒在分离和浓缩步骤中倾向于损失催化活性。这与循环使用的目的相反。认为催化活性的损失是由于缩聚物和焦炭沉淀到催化剂上。由于在催化剂分离和浓缩步骤期间温度和压力降低，从而产生了缩聚物和焦炭。在浆液催化剂加氢处理中，新鲜催化剂的费用必须与催化剂分离、催化剂浓缩和催化剂再生的费用相权衡。
美国专利5,298,152(引入作为参考)教导了无需再生或进行其它增强活性的处理，即将催化剂前体制成的活性催化剂循环至氢化区。当活性催化剂与产物分离时，其保持在基本与氢化区相同的条件下以避免缩聚物和焦炭的沉积。在该方法中，催化剂没有像将其从反应物分离时经常发生的那样迅速地失活。与本发明不同，Kramer教导了高压分离器可作用高压沉降器。在本发明中，催化剂从不允许沉降。
美国专利5,374,348教导了一种重烃油加氢裂化的方法，其中所述油与含硫酸铁添加剂颗粒的经过分馏的重油再循环液流混合。所述混合物然后向上通过反应器。反应器流出物进入热的分离器容器从而得到产物以及含有重质烃类和硫酸铁颗粒的液态烃流。重烃流进一步分馏得到沸点高于450℃含有添加剂颗粒的重油。该物料被循环返回到加氢裂化反应器。
发明概述
本发明涉及一种使用活性浆液催化剂组合物加氢转化重油的方法。
一种用于重油改质的方法，使用不允许沉降的浆液催化剂组合物，包括下列步骤：
(a)在改质反应器中，在加氢处理条件下，将重质原料、氢气、新鲜催化剂浆液组合物和循环浆液组合物混合；
(b)将改质反应器的排出流送至分离区，其中从塔顶排出沸点直到900℉的产物；
(c)将来自步骤(b)的残留在分离区中的物料送至不断搅拌着的催化剂储槽中；和
(d)将在不断搅拌着的催化剂储槽中的至少一部分物料送回到步骤(a)的改质反应器中。
本发明的优点包括：
-通过不允许催化剂沉降预防催化剂聚结(催化剂失活的来源)。
--从氢化区除去中间馏分油产物的塔顶馏分(作为气体蒸汽从热的高压分离器中除去)。
--来自氢化区的产物不含催化剂(不要求沉降、过滤、离心等)。
-当因为转化率为100％存在显著的压力和/或温度降时，没有催化剂显著的失活。
-生成非常少量的超缩物(supercondensates)(沥青质)和焦炭，对催化剂组合物的活性没有显著影响。
--在分离步骤中浓缩催化剂，无需进一步浓缩。
附图说明
附图说明了本发明的工艺步骤。
发明详述
本发明涉及使用活性浆液催化剂组合物加氢转化重油的方法，所述催化剂诸如在共同未决申请T-6344(S.N.    )和T-6393(S.N.    )中公开的那些。这些申请引入作为参考。这样的催化剂组合物包括VIB族金属化合物，例如钼。浆液催化剂组合物可以循环使用，仅采用单一分离步骤，不发生显著的催化剂失活。该单一分离步骤优选使用热高压分离器。
所述浆液催化剂组合物用于改质含碳原料，含碳的原料包括常压瓦斯油、减压瓦斯油、脱沥青油、烯烃、从焦油砂矿或沥青得到的油、从煤得到的油、重质原油、费-托法得到的合成油和从再循环油废料和聚合物得到的油。所述催化剂组合物非限制性地用于氢化改质的工艺过程，如热加氢裂化、加氢处理、加氢脱硫、加氢脱氮和加氢脱金属。催化剂用于使用固定床和沸腾床的工艺中。
本发明的方法可以用一段模式或二段模式操作。改质的反应器10(参见附图)仅表示了第一段。第二段(如果存在)可以是集成的加氢处理装置，在所述附图中未表示。在一段操作中，重油原料(管线25)与活性催化剂浆液和含氢的气体(管线5)在高温和高压下、在连续搅拌槽反应器中或沸腾床催化反应器中接触。活性催化剂浆液由多达95wt％的循环物料(管线30)和5wt％新鲜催化剂(管线15)组成。将所述原料、催化剂浆液和含氢气体在改质反应器10中混合，停留时间和温度足够达到可计量的热裂解率。来自改质反应器10的排出流通过管线35送至热高压分离器40。产物轻油与固体催化剂和未转化的重油在热高压分离器40中分离，然后通过管线45送至中间馏分油贮罐中。或者，可以将轻油送至第二段反应器(未显示)。该反应器一般是固定床反应器，用于油的加氢处理以进一步除去硫和氮从而改进产物特性。产物不含催化剂，不需要沉降、过滤、离心等。
在热高压分离器40中，基本上所有来自重油加氢转化改质区10的改质的产物作为气体-蒸汽流45从塔顶馏出。热高压分离器40底部液体主要由未转化的油和活性催化剂构成，经管线70将其送至循环催化剂储槽60。如述，该储槽用搅拌器55不断地搅拌，通过加入氢气(管线65)保持恒定的还原气氛。过量氢气通过排放流50除去。当需要之时，催化剂浆液被循环回改质反应器10(经管线30)。循环流可以构成高达95wt％的改质反应器中所用的催化剂。
通过以100％转化率运转改质工艺在整个改质、分离和存储期间保持至少最少的还原气氛，并且不允许催化剂组合物在任何时候沉降来保持催化剂的活性。在热高压分离器中分离后，不需要进一步的分离步骤。在整个方法中，可以容许显著的温度和压力波动，而仅有少量的超缩物和焦炭的沉淀物形成。在过去已使用的循环方法中，浆液催化剂组合物的积垢和失活显著。
                    工艺条件
对于所述的在改质反应器10中的第一段操作，重油原料的温度通常高于约700℉，优选高于750℉，最优选高于800℉以达到高转化率。氢分压的范围是350至4500psi，氢气对油的比在500至10,000SCFB。活性浆液催化剂在重油中的浓度通常为约100至20,000ppm，用金属(钼)的重量对重油原料重量表示。通常，更高的催化剂对油的比值会得到更高的硫、氮和金属的脱除转化率以及更高的裂化转化率。高压分离器的温度可以高达800℉。接近100％的脱金属转化率和1000℉以上的重油裂化转化率可以在合适的工艺条件下达到，而焦炭产率能够保持在小于约1％。
第二段(未在附图中表示)的工艺条件是典型的重油加氢处理条件。第二段反应器可以是固定床反应器、沸腾床反应器或移动床反应器。用于第二段反应器的催化剂是加氢处理催化剂，诸如含沉积在耐火金属氧化物上的VIB族和/或VIII族金属的那些。通过用该集成的加氢处理方法，成品油中硫和氮的含量可以非常低，还改进了成品油特性。
                    实施例
                    实施例1
该实施例描述了循环模式的重油加工(Athabasca减压渣油)。催化剂用共同未决申请S.N.＿＿＿(T-6393)公开的方法活化。催化剂仅用单一的油活化。
通过T-6393的方法制备的催化剂用于Athabasca真空残油(VR)和减压瓦斯油(VGO)原料在使用两个连续搅拌釜反应器的工艺设备中改质。催化剂和未转化的重油一起循环。使用97％Athabasca VR和3％Athabasca VGO的原料混合物。
Athabasca VR原料的特性如下表所列：
  在60/60下的API重力   3.9
  硫(wt％)   5.58
  氮(ppm)   5770
  镍(ppm)   93
  钒(ppm)   243
  碳(wt％)   83.57
  氢(wt％)   10.04
  MCRT(wt％)   17.2
  粘度212℉(cSt)   3727
  戊烷沥青质(wt％)   13.9
  沸点高于1050℉的馏分(wt％)   81
Athabasca VGO原料的特性如下表所列：
  在60/60下的API重力   15.6
  硫(wt％)   3.28
  氮(ppm)   1177
  碳(wt％)   85.29
  氢(wt％)   11.01
  MCRT(wt％)   0.04
  沸点高于650℉的馏分(wt％)   85
用于重油改质的工艺条件如下所列：
  总压(psig)   2500
  新鲜的Mo/新鲜的油比例(％)   0.24
  新鲜的Mo/总Mo比例   0.1
  新鲜的油/总油比例   0.75
  总原料LHSV   0.21
  反应器温度(℉)   825
  氢气流量(SCF/B)   9100
产品产率、特性和转化率列于下表：
  C4-气体(wt％)   12.1
  C5-180℉(wt％)   7.5
  180-350℉(wt％)   15.5
  350-500℉(wt％)   20.8
  500-650℉(wt％)   22.2
  650-800℉(wt％)   14.8
  800-1000℉(wt％)   3.9
  1000℉以上(wt％)   0.3
  HDN转化率(％)   62
  HDS转化率(％)   94
  HDM转化率(％)   99
  液体产品API重力   33
中间馏分油占产品的58.5wt％，杂原子含量彻底降低。
                    实施例2
该实施例描述了以循环模式重油改质(Hamaca减压渣油)。催化剂用共同未决申请S.N.＿＿＿(T-6393)公开的方法活化。催化剂仅用单一的油活化。通过T-6393所述方法制备的催化剂用于Hamaca减压残油(VR)和减压瓦斯油(VGO)原料在包括两个连续搅拌釜反应器和一个循环部分的工艺设备中改质，循环部分能够使催化剂与未转化的重油一起循环。使用90％Hamaca VR和10％Hamaca VGO的原料混合物。
HamacaVR原料的特性如下表所列：
  在60/60下的API重力   1.7
  硫(wt％)   4.56
  氮(ppm)   9222
  镍(ppm)   168
  钒(ppm)   714
  碳(wt％)   83.85
  氢(wt％)   9.46
  粘度266℉(cSt)   19882
  戊烷沥青质(wt％)   32
  沸点高于1050℉的馏分(wt％)   91
Hamaca VGO原料特性列于下表：
  在60/60下的API重力   14.2
  硫(wt％)   3.53
  氮(ppm)   2296
  碳(wt％)   84.69
  氢(wt％)   11.58
  沸点高于650℉的馏分(wt％)   89
用于重油改质的工艺条件如下所列：
  总压(psig)   2600
  新鲜的Mo/新鲜的油比例(％)   0.55
  新鲜的Mo/总Mo比例   0.25
  新鲜的油/总油比例   0.75
  总原料LHSV   0.16
  反应器温度(℉)   825
  氢气流量(SCF/B)   9400
产品产率、特性和转化率列于下表：
  C4-气体(wt％)   14
  C5-180℉(wt％)   6.6
  180-350℉(wt％)   15.4
  350-500℉(wt％)   21.1
  500-650℉(wt％)   22.4
  650-800℉(wt％)   12.6
  800-1000℉(wt％)   4
  1000℉以上(wt％)   1.5
  HDN转化率(％)   63
  HDS转化率(％)   96
  HDM转化率(％)   99
  液体产品的API重力   33
中间馏分油占产物的58.9wt％，杂原子含量彻底降低。

Claims (16)

1.一种重油改质方法，使用不允许沉降的浆液催化剂组合物，包括下列步骤：
(a)在改质反应器中，在加氢处理条件下，将重质原料、氢气、新鲜催化剂浆液组合物和循环浆液组合物混合；
(b)将改质反应器的排出流送至分离区，其中从塔顶排出沸点直到900°F的产物；
(c)将来自步骤(b)的残留在分离区中的物料送至不断搅拌着的催化剂储槽；和
(d)将在不断搅拌着的催化剂储槽中的至少一部分物料送回到步骤(a)的改质反应器中。
2.权利要求1的方法，其中重质原料选自常压瓦斯油、减压瓦斯油、脱沥青油、烯烃、从焦油砂矿或沥青得到的油、从煤得到的油、重质原油、费-托法得到的合成油和从再循环油废料和聚合物得到的油。
3.权利要求1的方法，其中所述改质方法选自热加氢裂化、加氢脱硫、加氢脱氮和加氢脱金属。
4.权利要求1的方法，其中分离区是热高压分离器。
5.权利要求1的方法，其中至少50wt％的产物在180°F和650°F范围内沸腾。
6.权利要求1的方法，其中改质反应器是持续搅拌釜反应器或沸腾床。
7.权利要求1的方法，其中循环浆液催化剂构成高达95wt％的改质反应器中所用的催化剂。
8.权利要求1的方法，其中加氢处理条件包括：温度大于750°F，氢气分压在350-4500psi范围内，氢气对油的比在500-10,000SCFB范围内。
9.权利要求1的方法，其中所述浆液催化剂组合物在重油中的浓度为100至20,000ppm，用金属的重量对重油原料重量表示。
10.权利要求1的方法，其中沸点低于900°F的产物不需进一步的脱除催化剂的分离过程。
11.权利要求1的方法，其中沸点低于900°F的产物被进一步改质以脱除杂原子。
12.权利要求10的方法，其中改质在选自移动床反应器、沸腾床反应器和固定床反应器的反应器中进行。
13.权利要求12的方法，其中改质在固定床反应器中进行。
14.权利要求1的方法，其中脱金属转化率为99％。
15.权利要求1的方法，其中焦炭产率小于1％。
16.权利要求1的方法，其中所述改质的方法是加氢处理。
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