CN1019585B - 铁-煤糊存在下的重质油加氢裂化 - Google Patents
铁-煤糊存在下的重质油加氢裂化Info
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Abstract
披露了一种在氢和铁-煤催化剂存在下将重质烃类油料转化的方法,其中的铁-煤催化剂是将煤颗粒和铁化合物颗粒在油中磨碎而制成一种糊状添加料,并将该煤-铁-油糊状料与该重质烃类油料混合,制备成加氢转化器的进料原料。
Description
本发明涉及烃类油料的加工,更具体讲是涉及在铁和煤添加料存在下,重质烃类油料的加氢裂化。
重质烃类油料通过加氢裂化过程转化成用作优质重整原料的轻质和中间馏分石脑油以及转化成燃料油和瓦斯油,在本技术领域已为公知。这些重质烃类油料可以是原油、常压焦油渣油、减压焦油渣油、重质循环油、页岩油、煤加工产生的液体物料、原油残渣油、拔顶原油以及从油砂提取的重质沥青油。值得特别注意的是从油砂提取得到的油,其中含很宽沸程的物料,从石脑油到煤油、瓦斯油、沥青等等,并含有大量沸点高于常压524℃的物料。
随着普通原油的储量逐渐减少,必须将这些重质油料加工以提高等级以应需求。在提高等级的过程中,把重质物料转化成轻质馏分,并需将大部分硫、氮和金属除去。
为此目的,可以采用焦化方法,例如延迟焦化或流化焦化,或者采用加氢方法,例如热法或催化法加氢裂化。焦化法的馏出物收率约70%(重量),并副产约23%(重量)的焦炭,它们已不适于用作燃料,因为氢∶碳比率很低,矿物质和硫的含量很高。
人们对另一类的高温和高压加氢方法已作了许多工作,已发现是很有希望的。在此方法中,将氢与重质油以向上流动方式通过空的管状反应器,反应器中无催化剂,并发现高分子量化合物能加氢和/或加氢裂化成为低沸程物料,同时发生脱硫、脱除金属和脱氮的反应。所用反应压力不超过24兆帕,温度不超过490℃。
在热法加氢裂化中,主要问题是焦炭或固体物沉积在反应器中,在较低压力操作时特别严重,其结果是被迫停工,造成巨大经济损失。较高压力可减轻反应器沾污。在24兆帕和470℃,基本上可消除焦炭沉积。但用高压操作的装置,投资和操作费用都很高。
人们已很清楚,原料中存在矿物质是发生焦炭沉积的重要原因。美国专利3,775,296指出,含矿物质更多的原料(3.8%,重量)与含矿物质较少的原料(<1%,重量)相比,前者在反应器中形成焦炭的趋向反而较小。其他的研究也表明,矿物质含量高对于沥青转化和脱硫没有明显影响,但能抑制在反应器中沉积焦炭和减轻反应器沾污。在美国专利3,151,057中建议加入焦炭载体,建议使用“收容剂(getter)”,例如砂、石英、矾土、镁氧矿、锆石、绿柱石或铁矾土。这些“收容剂”使用以后可以再生,可在约1090℃,在氧和水蒸汽中加热这些已沾污的载体,得到含相当多量氢气的再生产物气体。在1980年3月10日的加拿大专利1,073,389以及1980年7月29日的美国专利4,214,977中表明,加入煤或以煤为基础的催化剂,可使加氢裂化时减少焦炭沉积。所添加的煤起到焦炭前体沉积位点的作用,因而提供了把它们从系统中除去的机制。
使用这些以煤为基础的催化剂,可以在较低压力操作,并达到更高转化率。在加拿大专利1,073,389中描述了在煤催化剂中使用煤和Co、Mo和Al,在美国专利4,214,977中使用了铁-煤催化剂,在加拿大专利1,124,194中使用了飞灰。
在美国专利3,775,286中描述了一种煤加氢方法,该方法是把煤用水合氧化铁浸渍,或将干的水合氧化铁粉末与煤粉机械混合。加拿大专利1,202,588描述了在一种添加料存在下将重质油加氢裂化,该添加料的形式是煤与一种铁盐,例如硫酸铁的干混合物。然而,使用机械式混合物所达到的转化率很低,远低于用经浸渍的煤时的转化率。还有,将
铁和煤干法研磨和/或混合是一道危险而困难的工序。
本发明的目的是在重质烃原料中使用一种廉价并且只用一次不必回收的以碳为基础的添加料,用以克服加氢裂化过程中在反应器内产生沉积物的问题。
按本发明,是将一种铁化合物和煤或其他含碳物料在油中磨碎,从而制成一种糊状添加料,作为一种改进的铁-煤催化剂。该含碳物料和铁化合物可以在与油相混的条件下同时在一台磨碎机中进行混合,或者是将含碳物料与铁化合物分别混在油中并磨碎,然后将两种糊料混合到一起,成为铁-煤添加料。这种方法避免了干法磨碎和混合的问题,还避免了关系到湿法浸渍随后将煤颗粒干燥的问题。此外,当应用于重质烃类油料的加氢裂化时,能得到意想不到的改进的结果。
因此本发明的一个实施方案是使用包含重质烃类油料和铁-煤催化剂的糊状原料,在加氢转化条件下在加氢转化反应区进行加氢转化反应的过程,将至少一部分油转化成为低沸点产物,从而制成加氢转化的油料。在进料糊中铁-煤催化剂的存在量不超过5%(重量,以油料为基准)。按本发明,进料糊的制备是将含碳的(煤的)颗粒和铁化合物颗粒在油中一起磨碎,得到糊状添加料,其中含有煤颗粒和铁化合物颗粒,然后将所得煤-铁-油糊状物与重质烃类油料混合,成为进料糊。
此方法实质上避免了在反应区形成含碳沉积物。这些沉积物可能含有喹啉和苯不溶解的有机物质、矿物质、金属、硫以及少量苯可溶的有机物质,这些在后文中总称为“焦炭”沉积物。
本发明的方法特别适用于处理这样的重质油,即含有较大百分率,最好至少50%(体积)沸点高于524℃的重质油,以及可含有宽沸程物料,即从石脑油、煤油、瓦斯油一直到沥青的油料。本方法可以在较低压力操作,最适宜压力范围在3.5-24兆帕,而在加氢反应区不会生成焦炭。
虽然加氢裂化可以在多种已知的反应器(上流式或下流式)中进行,
特别适用的是使进料和气体向上流的管式反应器。反应器顶部的流出物最好在一个热分离器中分离,其气流可以送入低温-高压分离器,分离成为含氢和少量气态烃的气流和含有轻质油产物的液体产物流。
在添加料中使用的铁化合物通过氢和硫化氢的作用而转化成为硫化铁。所用铁化合物可以是氧化铁或一种铁盐,最好是用硫酸铁。该含碳物料最好是褐煤、副烟煤、煤矿不合格料或飞灰。
一种典型的添加料可含有10-90%(重量)该种铁盐,以及90-10%(重量)含碳物料。该添加料与重质油的混合比率,以重质油进料为基准,含有约0.1-5%(重量)。
制备此添加料的方便方法是使用一台磨碎机,在有油存在下将煤或其他含碳物料及铁盐磨碎成细颗粒。所用的油最好是本加工过程产生的重质瓦斯油,在磨碎时最好采用固体物含量高的混合物,固体物含量范围为10-60%(重量)。
这种磨碎机有一个重要优点,就是煤和铁可以磨碎至极小粒度。例如,很容易把粒度磨碎至小于75微米,并已发现,将粒度磨碎至10微米以下是特别有利的。
按一个优选实施方案,该铁-煤添加糊料与一种重质烃类进料油混合并与氢一起泵送通过立式反应器。从加氢裂化反应区顶部出来的气-液混合物可用多种方式分离。其中一种方法是在200-470℃和加氢裂化压力的热分离器中分离该气-液混合物。来自热分离器的重质烃类油产物可以再循环,或者送去二次加工。
从热分离器出来的气流中含有氢和混合烃气体,并在低温-高压分离器中进一步分离。借助于这种类型的分离器,所得的出口气流中大部分是氢和一些杂质,如硫化氢和小分子气态烃。这种气流通过一个气体
洗涤塔,经洗涤后的氢再循环,作为加氢裂化过程的一部分氢原料。通过调节涤气条件和加入补充氢气来保持再循环氢气的纯度。
低温-高压分离器中出来的液流是本方法的轻质烃类油产品,可以送去二次加工。
随着热分离器的重质油产物会带过来一些金属-煤添加料,它们将留在>524℃的沥青馏分中。但是,由于这是廉价的添加料,所以不必要回收,可以与该沥青一起烧掉或气化。在加氢裂化条件下,该金属盐是转化成为金属硫化物。
为了更清楚地了解本发明,由附图来说明本发明的一个优选实施方案。在这些图中,
图1是添加料制备的示意流程图;
图2是加氢裂化过程的示意流程图。
如图1所示,从矿场来的煤38在锤式粉碎机37中粉碎,得到最大粒度约8或16目(美国筛目)的碎煤,可贮于贮存仓31中。将已称重量的碎煤从仓31通过管路33送至带搅拌磨碎机32。已称重量的铁化合物从硫酸铁贮仓34经由管路33,或者直接送入磨碎机32。将所需量的油或残渣油39经由管路35送至管路33或送至磨碎机32。在磨碎机中制成的添加料/油糊40通过管路36送出,送至糊料贮槽(未示出)或送至加氢裂化装置进料处。
虽然图1所示是把煤和硫酸铁在32中同时磨碎,也可以把两者在各自的磨碎机中磨碎,然后用另一台磨碎机把两种糊料混合在一起。这种方式更容易控制粒度。
如图2的加氢裂化过程所示,将铁盐/煤的添加糊料与重质烃类进料油在进料槽10中混合成为糊状料。通过进料泵11和进料管路12而进入空反应塔13的底部。再循环氢气27与新鲜补充氢气28成为再循环气体而从管路30同时经管路12送入反应塔13。从塔顶部经由管路14排出气-液
混合物,送入热分离器15。从反应塔13出来的流出物在15中分离成为气流18和液流16。液流16是重质油产物,收集在17中。
按另一种方案,从管路16连一条支管路(未示出),经过泵(未示出)而进入进料管12,这条支管路用于再循环,将含有带出的金属硫化物颗粒和细煤粉的液流从分离器15再循环通入进料糊中,从而进入反应塔13。
还有另一种方案,将管路16通入一台旋流分离器(未示出),将金属硫化物颗粒和细煤粉与液流分开。分出的金属硫化物颗粒和细煤粉再循环到进料糊中而进入反应塔13,留下的液体收集在重质油产物容器17之中。
从热分离器15来的气流经管路18进入高压-低温分离器19。在此分离器中分出富氢气流,从管路22排出,轻质产物油通过管路20排出,并收集在容器21中。
富氢的气流22通过填料式洗涤塔23,在塔中用洗涤气油24洗涤,并经泵25和循环管路26构成循环。经洗涤的富氢气流从23排出,经管路27与来自28的新鲜补充氢气混合,通过再循环气体泵29和管路30而返回反应塔13。
由以下非限定性实例对本发明的一些优选实施方案进一步说明。
实例1
将Alberta产的Whitewood副烟煤在锤磨机中粉碎至粒度小于约8至16目,用于制备添加料。然后与硫酸铁及重质瓦斯油混合,混合比率为煤∶硫酸铁∶油=35∶15∶50,然后送入Drais Perl磨碎机或Szego磨碎机。所得糊状产物含有约50%固体物,干添加料的相当铁含量为9%(重量)。
为了进行对比,将200目的煤颗粒用七水合物形式的硫酸铁浸渍,然后按美国专利4,214,977的相同方式干燥。此种干添加料的铁含量为约9%(重量),水分含量低于2%。
按上述方法,制备出4种添加料,如表1所示。
表1
浸渍法 油/煤 油/煤 油/煤
磨碎料 磨碎料 磨碎料
#1 #2 #3
煤 Whitewood Alberta 同左 同左 同左
副烟煤
FeSO4七水合物 一水合物 同左 同左
油 - 重质瓦 同左 #5燃
斯油 料油
所用磨碎机 - Perl Szego Perl
将所得的添加料进行粒度分析,结果如表2所示
表2
粒度分布
浸渍法 #1 #2 #3
100-75微米 8 - 10 -
75-44微米 17 8 23 6
小于44微米 75 92 67 94
将以上添加料应用于具如下性质的重质烃类油料的加氢裂化:
表3
进料油性质-IPPL 1050°+(30IPPL84)
比重 API度 7.36
比重 15/15℃ 1.019
灰分 重量% 0.04
碳 重量% 86.4
氢 重量% 10.2
氮 重量% 0.47
硫 重量% 2.45
RCR 重量% 20.4
PI 重量% 20.2
TI 重量% 0.70
粘度 厘泊
100℃ 1889
150℃ 131.8
燃烧热值 千焦尔/千克 42400
V ppm(重量) 102
Ni ppm(重量) 55
Fe ppm(重量) 124
Ti ppm(重量) 3
Al ppm(重量) 53
Si ppm(重量) 18
Na ppm(重量) 46
K ppm(重量) 31
Ca ppm(重量) 19
Mg ppm(重量) 12
由上述原料油与1/2%或1%(重量)的混合添加料制备成混合糊状料,用作为小型加氢裂化试验装置的进料。该小型试验装置与图2所示连续式装置相似,处理量1桶/天,但没有所示气体洗涤塔和氢气再循环系统。
上述试验结果示于表4:
以上结果表明,本发明的添加料使用极低浓度时即对抑制反应器中沉积焦炭有很高效能。用它所达到的沥青转化率与使用同量的浸渍式煤催化剂相比时,至少是相同,或是超过。
实例2
制备由实例1所用的进料与2.5%(重量)的油/煤磨碎料的混合物,并将之用作为图2所示1桶/天小型装置的进料。
反应塔的操作条件如下:
试验#1 试验#2
反应塔温度,℃ 438 430-450
压力,兆帕 13.9 13.9
液时空速 0.55 0.60
再循环气体流量,米3/小时 4.03 4.03
再循环气体含氢量,%(体积) 85 85
以上试验所得结果如下:
试验#1 试验#2
沥青(>524℃)转化率,%(重量) 61.6 30.8-86.7
操作时间,天 18 18
焦碳沉积量,克 140 106
实例3
将实例1的进料以不同比率与实例1的#3油/煤磨碎料混合,并作为炼油厂的5000桶/天的加氢裂化装置的进料。所用操作条件和所得结果示于表5。
表5
天数 2 2 1 2 2 2
校正后操作条件
进料速率,桶/天 2680 3110 4020 4800 3030 3050
反应温度,℃ 350-460 350-460 350-460 350-460 350-460 350-460
压力,兆帕 13.9 13.9 13.9 13.9 13.9 13.9
进料中添加料
浓度,% 3.0 2.7 1.7 2.4 2.5 2.4
再循环气体含氢
量,%体积 85 85 85 85 85 85
产物净收率
气体,BFOE/D 400 560 570 660 600 470
石脑油,桶/天 450 540 690 820 610 500
馏出物,桶/天 860 870 1020 1000 1020 1020
减压瓦斯油,桶/天 760 1000 1390 1800 910 750
沥青,桶/天 820 990 1340 1610 590 860
总计
沥青转化率,
%重量 67 66 64 64 77 68
馏出物总收率,
%体积 82 82 80 80 95 83
Claims (10)
1、一种加氢转化方法,其中将包括一种重质烃类油料和一种铁-煤催化剂的进料原料于加氢转化条件下,在一个加氢转化反应区与一种含氢气体接触,将至少一部分所述油料转化成为较低沸点的产物,从而制出一种加氢转化的油料;所述铁-煤催化剂在所述进料糊状物中的存在量,按所述油料为基准为不超过5%(重量);其特征在于,通过将10-90%(重量)的选自褐煤、煤、副烟煤、煤矿不合格料及飞灰的含碳物料颗粒及90-10%(重量)的铁盐或铁的氧化物颗粒在油料中进行磨碎,制成一种颗粒度小于75微米的糊状添加料,然后将所述煤-铁-油糊状料与该重质烃类油料混合,成为所述的进料糊状物。
2、按权利要求1的方法,其特征在于在该添加料中的铁化合物的粒度是小于10微米。
3、按权利要求1的方法,其特征在于所述的铁盐是硫酸铁。
4、按权利要求1、2或3的方法,其特征在于该糊状添加料的制备是通过在球磨机或棒磨机中将煤、铁化合物以及油料磨碎而成。
5、按权利要求4的方法,其特征在于所述磨碎机是一种搅拌的球磨机。
6、按权利要求1、2或3的方法,其特征在于该糊状添加料的油料组分是一种重质瓦斯油。
7、按权利要求1、2或3的方法,其特征在于所述重质烃类油料含有至少50%(重量)沸点高于524℃的物料。
8、按权利要求1、2或3的方法,其特征在于所述含碳颗粒料和铁化合物是在同一个磨碎机中同时磨碎的。
9、按权利要求1、2或3的方法,其特征在于所述含碳颗粒料和铁化合物是在各自的磨碎机中分别磨碎,再将各磨碎机所得的糊状物混合到一起。
10、按权利要求1的方法,其特征在于所述糊状料是由10-60%(重量)的固体物所形成。
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CA557,988 | 1988-02-02 | ||
CA000557988A CA1317585C (en) | 1988-02-02 | 1988-02-02 | Hydrocracking of heavy oils in presence of iron-coal slurry |
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CN1019585B true CN1019585B (zh) | 1992-12-23 |
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US (1) | US4923838A (zh) |
JP (1) | JPH0611403B2 (zh) |
CN (1) | CN1019585B (zh) |
CA (1) | CA1317585C (zh) |
DE (1) | DE3903144C2 (zh) |
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CA1300068C (en) * | 1988-09-12 | 1992-05-05 | Keith Belinko | Hydrocracking of heavy oil in presence of ultrafine iron sulphate |
US5868923A (en) * | 1991-05-02 | 1999-02-09 | Texaco Inc | Hydroconversion process |
JP3467309B2 (ja) * | 1993-05-14 | 2003-11-17 | ジヤトコ株式会社 | バンドブレーキ装置 |
CN1053460C (zh) * | 1996-04-16 | 2000-06-14 | 中国石油化工集团公司 | 用于重、渣油催化加氢的分散型催化剂 |
US6004454A (en) * | 1995-11-22 | 1999-12-21 | China Petro-Chemical Corporation | Hydrocracking of heavy oil and residuum with a dispersing-type catalyst |
CN1045307C (zh) * | 1995-11-22 | 1999-09-29 | 中国石油化工总公司 | 重、渣油悬浮床加氢裂化方法 |
CA2190404C (en) * | 1995-11-22 | 2005-01-11 | Yuansheng Li | A dispersing-type catalyst for hydrocracking of heavy oil and residuum, the preparation and the use thereof |
US5935419A (en) * | 1996-09-16 | 1999-08-10 | Texaco Inc. | Methods for adding value to heavy oil utilizing a soluble metal catalyst |
US6059957A (en) * | 1996-09-16 | 2000-05-09 | Texaco Inc. | Methods for adding value to heavy oil |
US5807478A (en) * | 1997-05-16 | 1998-09-15 | Exxon Research And Engineering Company | Bitumen modification using fly ash derived from bitumen coke |
US6517706B1 (en) * | 2000-05-01 | 2003-02-11 | Petro-Canada | Hydrocracking of heavy hydrocarbon oils with improved gas and liquid distribution |
CN100457261C (zh) * | 2005-04-27 | 2009-02-04 | 中国石油化工股份有限公司 | 一种铁基煤液化催化剂及其制备方法 |
US8123934B2 (en) * | 2008-06-18 | 2012-02-28 | Chevron U.S.A., Inc. | System and method for pretreatment of solid carbonaceous material |
US8372773B2 (en) * | 2009-03-27 | 2013-02-12 | Uop Llc | Hydrocarbon conversion system, and a process and catalyst composition relating thereto |
US20110120916A1 (en) * | 2009-11-24 | 2011-05-26 | Chevron U.S.A. Inc. | Hydrogenation of solid carbonaceous materials using mixed catalysts |
US20110120917A1 (en) * | 2009-11-24 | 2011-05-26 | Chevron U.S.A. Inc. | Hydrogenation of solid carbonaceous materials using mixed catalysts |
US20110120915A1 (en) * | 2009-11-24 | 2011-05-26 | Chevron U.S.A. Inc. | Hydrogenation of solid carbonaceous materials using mixed catalysts |
US20110120914A1 (en) * | 2009-11-24 | 2011-05-26 | Chevron U.S.A. Inc. | Hydrogenation of solid carbonaceous materials using mixed catalysts |
US8992765B2 (en) | 2011-09-23 | 2015-03-31 | Uop Llc | Process for converting a hydrocarbon feed and apparatus relating thereto |
US9321037B2 (en) * | 2012-12-14 | 2016-04-26 | Chevron U.S.A., Inc. | Hydroprocessing co-catalyst compositions and methods of introduction thereof into hydroprocessing units |
CN104549276B (zh) * | 2013-10-28 | 2017-04-26 | 中国石油化工股份有限公司 | 一种渣油临氢热裂化催化剂及其制备和应用 |
WO2017058972A1 (en) | 2015-09-30 | 2017-04-06 | Uop Llc | Process for using iron and particulate carbon catalyst for slurry hydrocracking |
CN107683321B (zh) | 2015-09-30 | 2021-07-02 | 环球油品公司 | 使用铁和钼催化剂进行淤浆加氢裂化的方法 |
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US2572061A (en) * | 1948-09-16 | 1951-10-23 | Texaco Development Corp | Process for the hydrogenation of coal |
US3755137A (en) * | 1971-03-24 | 1973-08-28 | Hydrocarbon Research Inc | Multi-stage ebullated bed coal-oil hydrogenation and hydrocracking process |
JPS5373486A (en) * | 1976-12-13 | 1978-06-29 | Nittetsu Kagaku Kogyo Kk | Manufacture of catalyst for coal liquefaction |
DE2735829A1 (de) * | 1977-08-09 | 1979-02-22 | Metallgesellschaft Ag | Verfahren zur erzeugung von kohlenwasserstoffen aus kohle |
CA1094492A (en) * | 1977-10-24 | 1981-01-27 | Ramaswami Ranganathan | Hydrocracking of heavy oils using iron coal catalyst |
CA1163222A (en) * | 1981-02-12 | 1984-03-06 | Her Majesty The Queen, In Right Of Canada As Represented By The Minister Of Natural Resources Canada | Simultaneous demetalization and hydrocracking of heavy hydrocarbon oils |
ZA822184B (en) * | 1981-04-08 | 1983-11-30 | British Petroleum Co Plc | Hydrogenation catalyst |
CA1151579A (en) * | 1981-10-07 | 1983-08-09 | Ramaswami Ranganathan | Hydrocracking of heavy hydrocarbon oils with high pitch conversion |
US4437972A (en) * | 1982-02-08 | 1984-03-20 | Mobil Oil Corporation | Process for co-processing coal and a paraffinic material |
US4557822A (en) * | 1982-12-27 | 1985-12-10 | Exxon Research And Engineering Co. | Hydroconversion process |
US4486293A (en) * | 1983-04-25 | 1984-12-04 | Air Products And Chemicals, Inc. | Catalytic coal hydroliquefaction process |
-
1988
- 1988-02-02 CA CA000557988A patent/CA1317585C/en not_active Expired - Fee Related
-
1989
- 1989-02-01 US US07/304,557 patent/US4923838A/en not_active Expired - Fee Related
- 1989-02-01 JP JP1023653A patent/JPH0611403B2/ja not_active Expired - Lifetime
- 1989-02-01 CN CN89100660.5A patent/CN1019585B/zh not_active Expired
- 1989-02-02 DE DE3903144A patent/DE3903144C2/de not_active Expired - Fee Related
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CN1035836A (zh) | 1989-09-27 |
DE3903144C2 (de) | 1998-03-19 |
CA1317585C (en) | 1993-05-11 |
JPH0611403B2 (ja) | 1994-02-16 |
US4923838A (en) | 1990-05-08 |
JPH026853A (ja) | 1990-01-11 |
DE3903144A1 (de) | 1989-08-10 |
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