CN106179376B - 一种高活性重馏分油加氢处理催化剂的制备方法 - Google Patents
一种高活性重馏分油加氢处理催化剂的制备方法 Download PDFInfo
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- CN106179376B CN106179376B CN201610507552.0A CN201610507552A CN106179376B CN 106179376 B CN106179376 B CN 106179376B CN 201610507552 A CN201610507552 A CN 201610507552A CN 106179376 B CN106179376 B CN 106179376B
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 13
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明为一种高活性重馏分油加氢处理催化剂的制备方法，包括：选用VIII族金属镍的可溶盐与多羟基酸络合剂一起配成酸性溶液；选用VIB族金属钼的可溶盐与碱性沉淀剂一起配成碱性溶液；以大孔拟薄水铝石、纳米二氧化钛粉末与硅溶胶混配成的悬浊态浆液为基底，并流加入酸性溶液、碱性溶液进行密闭反应，使金属组分在钛‑硅‑铝介质中均匀分散，反应结束后，经过滤、洗涤得到催化剂前驱体滤饼，经熟化、成型、干燥、焙烧得到成品催化剂。与现有方法制备的体相加氢催化剂相比，该方法制备的催化剂具有机械强度高、磨耗低，孔容大、金属分散度高，加氢活性好、使用寿命长等优点，特别适合于硫氮含量高、稠环芳烃比例大，难于加工的劣质重馏分油的加氢处理。
Description
技术领域
本发明属于炼油领域，具体涉及一种高活性重馏分油加氢处理催化剂的制备方法。
背景技术
随着国内外环保法规的日趋严格，炼油企业面临着更加严格的清洁燃料生产挑战，柴油的无硫化已经成为世界各国和地区柴油新标准的发展趋势，而炼厂出于经济效益和投资成本的考虑，又希望加氢装置可在更低的操作压力和反应温度下实现尽可能高的原料加工量，这就需要研究者开发出更高活性的加氢催化剂来应对不断提高的环保要求和市场需求。目前工业上使用的柴油加氢催化剂主要是负载型的Ni-Mo、Co-Mo、Ni-W等过渡金属硫化物催化剂，由于受到金属负载量的限制，现有的负载型催化剂很难实现加氢活性的大幅提高，因此近年来非负载型加氢催化剂的研究一直是本领域的一大热点。
体相催化剂相对于负载型催化剂来说，通过制备方法的改变，解决了催化剂对不具被加氢性能的载体组分的依赖，实现催化剂直接由活性金属或主要由活性金属构成，从而具有更高的本征活性。雅宝催化剂公司基于“体相催化剂”的设计理念开发的Nebula催化剂，已在多套轻油深度加氢脱硫装置上工业应用，其脱硫、脱氮和脱芳烃活性达到常规负载型催化剂的2～3倍。但是，就目前此类催化剂的工业应用情况来看，由于体相催化剂摒弃了传统的氧化铝载体结构直接由金属制备，从而使催化剂的孔容、比表面积大幅降低，催化剂孔道尺寸减小，没有支撑结构导致催化剂机械强度和抗磨损能力较差，使得此类催化剂在对大分子硫、氮和芳烃化合物含量较高的重馏分油以及劣质二次加工馏分油的加氢处理中使用受到限制。
US4880526公开了一种含Ni、Mo、W、Co用于加氢处理的高活性体相催化剂及其制备方法。该方法先制备氧化铝胶体，然后加入含活性金属组分可溶性盐类进行混合，干燥、焙烧得到体相催化剂。另外还可采取先制备出氧化铝胶体，经干燥后，与含活性金属组分非可溶性盐类进行混合、干燥、焙烧。这种方法可实现催化剂中金属含量的提高，但活性金属不同组分以及氧化铝组分间仅通过机械混合粘结，不能形成有效配伍，导致金属分布不均匀，活性利用率较低。
CN101468309公开了一种非负载加氢催化剂的制备方法。该方法将至少一种VIII族非贵金属化合物的溶液与至少一种VIB族金属化合物的溶液接触得到浆液，对该浆液进行水热处理制备体相加氢催化剂。该方法的优点在于操作流程简单，易于生产放大，但也存在着不同金属组分间通过反应结合不充分，主金属与助金属的协同作用不能充分发挥的不足。
US6299760公开了一种较为优异的用于加氢处理的体相催化剂及其制备方法，该方法先通过金属共沉淀制备Ni-Mo或Ni-Mo-W组合物，干燥后制成金属粉末，再用氧化铝粘接或与氧化铝胶体混合后脱水、挤条、干燥。由于该方法制备的催化剂金属含量高，但金属和氧化铝间缺乏足够的相互作用会导致催化剂强度差，且Ni-Mo或Ni-Mo-W前驱体以金属粉末形态进行利用，必然导致部分金属不能被充分利用造成活性损失。
CN101722007A公开了一种加氢催化剂组合物的制备方法。该方法包括：(1)共沉淀法制备NixWyOz复合氧化物前身物；(2)NixWyOz复合氧化物前身物与MoO3打浆混合、过滤；(3)成型、活化为最终催化剂。由该方法制备体相加氢催化剂，制备方法简便，金属损失率低，催化剂活性高，但由于活性组分缺乏有效的支撑结构，催化剂存在强度不高，易磨损，使用寿命低的问题。
发明内容
本发明的目的是在现有技术的基础上，提供一种高活性重馏分油加氢处理催化剂的制备方法，特别是一种非负载型重馏分油加氢处理催化剂的制备方法。
传统的负载型加氢催化剂由于受到金属负载量的限制，加氢活性很难在现有基础上实现大幅的提升，这为非负载型催化剂的研制及工业应用提供了广阔的前景。但目前非负载型或体相型催化剂的工业应用量十分有限，传统的负载型加氢催化剂仍是市场的主流，这主要由于以下几个方面的原因：一、非负载型催化剂因为缺乏有效的支撑结构，导致催化剂的机械强度、磨耗等物性不能满足工业装置的使用需求；二、非负载型催化剂由于孔容、孔径偏小，不适用于劣质重馏分油的加氢处理；三、非负载型催化剂由于制备成本高导致售价较高，对于多数炼厂来说使用非负载型催化剂的经济性并不明显。
为此，本发明从解决以上三方面技术问题的角度入手，通过在制备过程中引入钛-硅-铝支撑结构提升催化剂的强度，并利用钛-硅-铝组分与活性金属的结合及配伍，优化活性相结构，改善金属分散状态，提高金属的利用率，充分发挥金属活性，从而降低成本。同时，大孔的氧化铝结构有利于大分子硫、氮、芳烃化合物在催化剂中的扩散，为催化剂在重馏分油加氢处理方面提供应用基础。
本发明为一种高活性重馏分油加氢处理催化剂的制备方法，其特征在于，包括以下步骤：
a.选用VIII族过渡金属镍的可溶盐与络合剂配制成酸性溶液；所述的络合剂为多羟基酸、乳酸、马来酸、琥珀酸或草酸；
b.选用VIB族过渡金属钼的可溶盐与碱性沉淀剂配成碱性溶液；
c.选用大孔拟薄水铝石、纳米二氧化钛粉末加入硅溶胶中，在室温下下高速搅拌配成悬浊态浆液；
d.采用带搅拌和控温装置的玻璃合成釜将步骤a中的酸性溶液和步骤b中的碱性溶液并流加入步骤c制备的浆液中，搅拌下进行沉淀反应，沉淀反应温度为40～90℃，反应时间0.5～3h；反应结束后滤除母液，对滤饼进行洗涤处理；
e.将洗涤除去杂离子后的滤饼与胶溶剂、粘结剂、扩孔剂和去离子水混合，经熟化、成型、干燥、焙烧得到成品催化剂；
所述的成品催化剂中，氧化钛含量为3～12wt％，氧化硅含量为5～15wt％，氧化铝含量为10～40％，氧化镍含量为10～30wt％，氧化钼含量30～60wt；催化剂的孔容≮0.35mL/g，比表面积为≮140m2/g，机械强度≮150N/cm。催化剂外形优选为三叶草、蝶形或齿球形。
根据本发明所述的制备方法，其中镍的可溶盐优选为乙酸镍，多羟基酸络合剂优选为柠檬酸、酒石酸、苹果酸中的一种或几种；钼的可溶盐为钼酸铵或氧化钼，碱性沉淀剂为氨水、碳酸铵、碳酸氢铵、氢氧化钠、碳酸钠或碳酸钾中的一种或几种。
所述的胶溶剂为硝酸或乙酸；所述的粘结剂为羟甲基纤维素或田菁粉；所述的扩孔剂为聚合度1000～20000的聚乙烯醇、聚合度500～10000的聚乙二醇或聚合度500～2000的聚丙二醇等聚醚多元醇中的一种或几种。
根据本发明所述的制备方法，其中所述的大孔拟薄水铝石的孔容≮1.2ml/g，6～12nm孔径分布≮85％。
本发明还提供了一种上述的制备方法制得的催化剂经硫化还原后在焦化蜡油(CGO)、减压蜡油(VGO)等重质馏分油或劣质馏分油的中高压加氢预处理中的应用，可实现重、劣质原料的深度脱硫、脱氮及芳烃饱和。
本发明提供的催化剂制备方法，与传统负载型加氢催化剂制备方法相比，具有金属载量大，催化剂活性大幅提升的优点；与现有的体相加氢催化剂制备方法相比，本发明方法制备的催化剂具有机械强度高、磨耗低，孔容大、金属分散度高，加氢活性好、使用寿命长等优点，特别适合于硫氮含量高、稠环芳烃比例大，难于加工的劣质重馏分油的加氢处理。
附图说明
图1为本发明高活性重馏分油加氢处理催化剂活性相分散状态透射电镜图。
具体实施方式
以下将通过具体的实施例进一步阐述本发明的特征，但不局限于以下实施例。以下涉及的百分比均为重量百分比。
实施例1
取乙酸镍40g，草酸20g，加入去离子水中搅拌溶解，定容至300mL备用，记为A-1；取氧化钼84g，加入198g氨水中，搅拌溶解并以去离子水定容至300mL备用记为B-1；取大孔拟薄水铝石108g，纳米二氧化钛粉末13g，加入125mL硅溶胶中，将搅拌桨转速调至300r/min，搅拌打浆30min，得到浆液C-1。
将浆液C-1加热至60℃，保持温度恒定，搅拌下将溶液A-1和溶液B-1并流匀速加入浆液C-1中，密闭进行沉淀反应1.5h，反应结束后滤除母液，使用去离子水对滤饼进行洗涤。
将洗涤除去杂离子后的滤饼置于轮式混碾机中，加入硝酸6g、田菁粉5g、聚合度为2000的聚丙二醇8g以及去离子水150g，混碾熟化15min后取出，再放入挤条机中挤压成Φ1.5mm四叶草条型，将小条晾晒24h后，于120℃下干燥4h，600℃焙烧3h，得到成品催化剂，记为Sample-1，催化剂物性见表1。
实施例2
取乙酸镍48g，酒石酸39g，加入去离子水中搅拌溶解，定容至300mL备用，记为A-2；取仲钼酸铵122g，碳酸钠33g，加入去离子水中搅拌溶解后，定容至300mL备用，记为B-2；取大孔拟薄水铝石86g，纳米二氧化钛粉末10g，加入100mL硅溶胶中，将搅拌桨转速调至300r/min，搅拌打浆30min，得到浆液C-2。
将浆液C-2加热至60℃，保持温度恒定，搅拌下将溶液A-2和溶液B-2并流匀速加入浆液C-2中，密闭进行沉淀反应1h，反应结束后滤除母液，使用去离子水对滤饼进行洗涤。
将洗涤除去杂离子后的滤饼置于轮式混碾机中，加入硝酸6g、田菁粉5g、聚合度为20000的聚乙烯醇6g以及去离子水150g，混碾熟化15min后取出，再放入挤条机中挤压成Φ1.5mm四叶草条型，将小条晾晒24h后，于120℃下干燥4h，600℃焙烧3h，得到成品催化剂，记为Sample-2，催化剂物性见表1。
实施例3
取乙酸镍56g，苹果酸45g，加入去离子水中搅拌溶解，定容至300mL备用，记为A-3；取仲钼酸铵142g，氢氧化钠39g，加入去离子水中搅拌溶解后，定容至300mL备用，记为B-3；取大孔拟薄水铝石65g，纳米二氧化钛粉末8g，加入75mL硅溶胶中，将搅拌桨转速调至300r/min，搅拌打浆30min，得到浆液C-3。
将浆液C-3加热至60℃，保持温度恒定，搅拌下将溶液A-3和溶液B-3并流匀速加入浆液C-3中，密闭进行沉淀反应0.5h，反应结束后滤除母液，使用去离子水对滤饼进行洗涤。
将洗涤除去杂离子后的滤饼置于轮式混碾机中，加入硝酸6g、田菁粉5g、聚合度为10000的聚乙二醇6g以及去离子水150g，混碾熟化15min后取出，再放入挤条机中挤压成Φ1.5mm的四叶草条型，将小条晾晒24h后，于120℃下干燥4h，600℃焙烧3h，得到成品催化剂，记为Sample-3，催化剂物性见表1。
表1
实施例4-6
本实例说明本发明提供的催化剂对于重、劣质馏分油的加氢反应性能。
采用炼厂焦化装置重馏分油与催化裂化装置劣质柴油馏分按6:4的比例混合作为反应原料，原料主要性质见表2。
采用100mL的固定床加氢装置分别对催化剂Sample-1、Sample-2、Sample-3进行加氢反应性能评价，催化剂床层上端装填等量的加氢保护剂。
催化剂硫化条件：使用含3％CS2的航煤，在空速1.0h-1，氢油体积比500:1，压力8.5MPa的压力下，对催化剂进行预硫化。
硫化升温程序：在120℃下进预硫化油，稳定2h；以15℃/h升温至150℃，恒温硫化4h；以6℃/h升温至230℃，恒温硫化10h；以6℃/h升温至290℃，恒温硫化6h；以10℃/h升温至340℃，恒温硫化6h；最后自然降温至200℃，切换反应原料。
反应操作条件：压力8.5MPa，平均反应温度360℃，氢油体积比800：1，体积空速为1.0h-1。评价结果见表2。
对比例1
本对比例说明通过本发明方法制备的催化剂与现有工业参比剂的性能对比。选用当前在多家炼厂应用的Ni-Mo/Al2O3负载型工业催化剂作为参比，进行反应活性对比，参比催化剂记为Reference-1，参比剂的评价实验采用与实施例4相同的方法进行，催化剂评价结果见表2。
对比例2
本对比例说明通过本发明方法制备的催化剂与现有工业参比剂的性能对比。选用国内已工业应用的Ni-Mo-W型体相催化剂作为参比，进行反应活性对比，参比催化剂记为Reference-2，参比剂的评价实验采用与实施例4相同的方法进行，催化剂评价结果见表2。
表2
由表2中的对比评价结果可见，按照本发明方法制备的催化剂在用于重、劣质馏分油加氢反应时，具有比工业参比剂更加优异的加氢处理性能。
Claims (5)
1.一种高活性重馏分油加氢处理催化剂的制备方法，其特征在于，包括以下步骤：
a.选用VIII族过渡金属镍的可溶盐与络合剂配制成酸性溶液；所述的络合剂为多羟基酸、乳酸、马来酸、琥珀酸或草酸；
b.选用VIB族过渡金属钼的可溶盐或氧化钼与碱性沉淀剂配成碱性溶液；
c.选用大孔拟薄水铝石、纳米二氧化钛粉末加入硅溶胶中，在室温下高速搅拌配成悬浊态浆液；
d.采用带搅拌和控温装置的玻璃合成釜将步骤a中的酸性溶液和步骤b中的碱性溶液并流加入步骤c制备的悬浊态浆液中，搅拌下进行沉淀反应，沉淀反应温度为40～90℃，反应时间0.5～3h；反应结束后滤除母液，对滤饼进行洗涤处理；
e.将洗涤除去杂离子后的滤饼与胶溶剂、粘结剂、扩孔剂和去离子水混合，经熟化、成型、干燥、焙烧得到催化剂；
所述的催化剂中，氧化钛含量为3～12wt％，氧化硅含量为5～15wt％，氧化铝含量为10～40％，氧化镍含量为10～30wt％，氧化钼含量30～60wt％；催化剂的孔容≮0.35mL/g，比表面积为≮140m2/g，机械强度≮150N/cm。
2.按权利要求1所述的制备方法，其特征在于，所述的催化剂外形为三叶草、蝶形或齿球形。
3.按权利要求1所述的制备方法，其特征在于，所选用的大孔拟薄水铝石孔容≮1.2ml/g，6～12nm孔径分布≮85％。
4.按权利要求1所述的制备方法，其特征在于，所述的镍的可溶盐为乙酸镍，多羟基酸为柠檬酸、酒石酸、苹果酸中的一种或几种；钼的可溶盐为仲钼酸铵，碱性沉淀剂为氨水、碳酸铵、碳酸氢铵、氢氧化钠、碳酸钠和碳酸钾中的一种或几种；
所述的胶溶剂为硝酸或乙酸；所述的粘结剂为羟甲基纤维素或田菁粉；所述的扩孔剂为聚合度1000～20000的聚乙烯醇、聚合度500～10000的聚乙二醇和聚合度500～2000的聚丙二醇聚醚多元醇中的一种或几种。
5.一种按权利要求1所述的制备方法制得的催化剂经硫化还原后在重质馏分油或劣质馏分油的中高压加氢预处理中的应用。
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