CN114436304B - 一种球形氧化铝载体的制备方法 - Google Patents
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 44
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000005096 rolling process Methods 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 24
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- 235000019270 ammonium chloride Nutrition 0.000 abstract description 12
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
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- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
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- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
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- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
- C01F7/442—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination in presence of a calcination additive
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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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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Abstract
本发明公开了一种球形氧化铝载体的制备方法，包括如下内容：将拟薄水铝石A与氯化铵混合，得到物料W1；（2）将拟薄水铝石B与氯化铵混合，得到物料W2；（3）将物料W1经滚球成型，得到球形前驱体I；（4）将物料W2与球形前驱体I混合，进行滚球成型，然后干燥、焙烧，得到球形氧化铝载体。本发明方法制备的氧化铝载体孔道结构呈不均匀分布，即载体表面孔道较大，载体内部孔道较小，该载体适用于制备重油加氢催化剂。
Description
技术领域
本发明属于催化剂材料制备领域，具体地涉及一种球形氧化铝载体的制备方法。
背景技术
近年来，随着原油资源的重质化，对燃料油消费需求的增长和环保法规的日益严格，采用加氢技术将渣油转化为优质轻质燃料油和化工产品，有助于提高原油加工深度、减少环境污染、提高轻质油收率和改善产品质量等。渣油富集原油中大部分的杂原子，如硫、氮和金属( 主要是Ni 和V) 等。渣油中的金属主要存在于胶质和沥青质等大分子化合物中，这部分化合物结构复杂，分子尺寸大，扩散困难。Ni 和V 等金属将在催化剂孔道内逐渐沉积，覆盖在催化活性位上，并堵塞催化剂孔道导致催化剂最终完全失活，因此必须先进行加氢脱除，以免毒化下游的加氢脱硫和催化裂化催化剂等。因此，为了达到最大化渣油加氢脱金属性能，要求催化剂具备合理孔道分布，能够有效改善大分子反应物的传质扩散、反应和金属沉积。
目前，常用的加氢催化剂是以氧化铝或含有少量助剂的氧化铝载体，形状以三叶草、蝶形和圆柱形为主，这类催化剂具有成型效率高、生产量大的特点。但由于其流动性能差，难实现均匀的密相装填，导致催化剂床层不稳定，产生沟流。球形催化剂具有流动性能好，磨损小，同时装剂和卸剂过程方便。
CN106311351A公开一种球形氧化铝载体及其制备方法，该方法首先将第一原料粉与粘结剂进行混合造粒，形成粒径为0.1-3mm的湿球；然后将第二原料粉与上述形成的湿球接触，再依次进行预干燥、干燥、过筛以及焙烧；其中，所述第一原料粉与所述第二原料粉相同或不相同，各自为拟薄水铝石或拟薄水铝石与薄水铝石的混合物。该方法制备的球形氧化铝载体具有较高的机械强度，球形氧化铝载体表面孔径较小，不利于渣油大分子反应物向载体内部的扩散。
CN103041868A公开一种球形催化剂载体的制备方法，该方法通过向氧化铝前身物中分别加入阴离子表面活性剂和阳离子表面活性剂的方式，改善了氧化铝载体表面的物理性质，调节了载体成型过程中物料的粘连性、流变性，降低了载体成型后的塑变性，大幅度提高了球形载体的收率。该方法制备的氧化铝载体孔径较小，不适合重渣油的加氢反应。
发明内容
针对现有技术的不足，本发明提供一种球形氧化铝载体的制备方法。本发明方法制备的氧化铝载体孔道结构呈不均匀分布，即载体表面孔道较大，载体内部孔道较小，该载体适用于重渣油加氢等涉及大分子参与的反应过程。
本发明的球形氧化铝载体的制备方法，包括如下内容：
（1） 将拟薄水铝石A与NH4Cl混合，得到物料W1；
（2）将拟薄水铝石B与NH4Cl混合，得到物料W2；
（3）将物料W1经滚球成型，得到球形前驱体I；
（4）将物料W2与球形前驱体I混合，进行滚球成型，然后干燥、焙烧，得到球形氧化铝载体。
本发明方法中，步骤（1）所述的拟薄水铝石A可以是任意方法制备的拟薄水铝石，比如采用沉淀法、醇铝水解法、无机盐溶胶-凝胶法、水热法、气相沉积法等方法制备。拟薄水铝石的孔容为0.6-1.2mL/g，比表面积为150-310m2/g，可几孔径为10-20nm。
本发明方法中，步骤（1）所述NH4Cl可以为粉末或小晶粒，加入量以铵根计与拟薄水铝石以铝元素计的摩尔比为1:15-1:10，优选1:12-1:10；二者混合均匀。
本发明方法中，步骤（2）所述的拟薄水铝石B可以是任意方法制备的拟薄水铝石，比如采用沉淀法、醇铝水解法、无机盐溶胶-凝胶法、水热法、气相沉积法等方法制备。拟薄水铝石的孔容为0.8-1.5mL/g，比表面积为180-350m2/g，可几孔径为15-30nm。
本发明方法中，步骤（2）所述NH4Cl可以为粉末或小晶粒，加入量以铵根计与拟薄水铝石以铝元素计的摩尔比为1:10-1:4，优选1:8-1:5；二者混合均匀。
本发明方法中，所述的滚球成型在转盘成型机中进行，所述的转盘成型机转动操作条件为：转盘的倾角为40-70º，转盘的转速为10-30rpm；物料在转盘内的成型时间为5-30min。成型过程中向物料中喷入将含胶溶剂的水溶液；所述的含胶溶剂的水溶液为硝酸、磷酸、草酸、醋酸的水溶液中的一种或几种混合，溶液的质量浓度为1%-3%，优选为醋酸的水溶液。
本发明方法中，步骤（4）所述的干燥时间为1-5小时，优选2-4小时，干燥温度为60℃-180℃，优选为80℃-150℃；所述的焙烧温度为450-850℃，优选500-750℃，焙烧时间为2-6小时，优选2-4小时。
本发明方法制备的球形氧化铝载体在重渣油加氢工艺中的应用，一般的工艺条件为：反应温度370-410℃，氢分压12-18MPa，液时体积空速0.1-1.5h-1，氢油体积比500-2000：1。
与现有技术相比较，本发明制备的球形氧化铝载体具有以下优点：
1、本发明使用两种具有不同孔道结构的拟薄水铝石为原料进行滚球成型，可几孔径相对较小的拟薄水铝石作为球核，可几孔径相对较大的拟薄水铝石作为球壳，首先从原料角度出发，保证了载体表面即球壳的孔径相对较大，载体内部即球核的孔径相对较小。
2、两种拟薄水铝石与NH4Cl混合均匀后滚球成型，研究发现，氯化铵焙烧时产生的氨气和氯化氢可以起到冲孔作用，提高了载体内部与表面孔道的贯通性。另一方面，生成的氨气和氯化氢可与氧化铝晶粒发生作用，改变氧化铝粒子的晶粒尺寸及粒子的堆积状态，起到扩大氧化铝孔道的作用，即可同时提高载体内部及表面的可几孔道。
3、该方法制备过程简单，易于工业化生产。
具体实施方式
下面结合实施例来进一步说明本发明的技术方案，但并不局限于以下实施例。本发明中，wt%为质量分数。
应用N2物理吸-脱附表征实施例与对比例样品孔结构，具体操作如下：采用ASAP-2420型N2物理吸-脱附仪对样品孔结构进行表征。取少量样品在300℃下真空处理3-4小时，最后将产品置于液氮低温（-200℃）条件下进行氮气吸-脱附测试。其中比表面积根据BET方程得到，孔容和孔直径在100nm以下的分布率根据BJH模型得到。
本发明方法中使用的拟薄水铝石A1的性质如下：孔容为0.75mL/g，比表面积为223m2/g，可几孔径为12.5nm。
本发明方法中使用的拟薄水铝石A2的性质如下：孔容为0.83mL/g，比表面积为252m2/g，可几孔径为15nm。
本发明方法中使用的拟薄水铝石B的性质如下：孔容为1.2mL/g，比表面积为335m2/g，可几孔径为25nm。
实施例1
（1）称取适量拟薄水铝石A1，加入适量氯化铵，控制铵根离子与铝离子
的摩尔比为1:12.5，将上述物料混合均匀得到物料W1。
（2）称取适量拟薄水铝石B，加入适量氯化铵，控制铵根离子与铝离子
的摩尔比为1:6.5，将上述物料混合均匀得到物料W2。
（3）将适量步骤（1）物料W1置于转盘成型机内，调节转盘的倾角为55º，转盘的转速为20rpm；经喷雾器将质量浓度为1.5%的醋酸水溶液喷洒到转盘内的氧化铝成型物料W1上经混合接触后，物料在转盘内的成型时间为30min，得到直径1.0～1.5mm的球形前驱体I；
（3）将适量步骤（2）物料W2和步骤（3）制备的球形前驱体I置于转盘成型机内充分混合，调节转盘的倾角为60º，转盘的转速为10rpm，经喷雾器将质量浓度为1.5%的醋酸水溶液喷洒到转盘内的物料上经混合接触后，物料在转盘内的成型时间为10min，得到直径1.5～2.0mm的球形物料，将所得球形物料经过120℃干燥3h，650℃焙烧4h后，得到球形氧化铝载体S-1，载体性质见表1。
实施例2
同实施例1，只是物料W1拟薄水铝石A1换成拟薄水铝石A2，混合物料中铵根离子与铝离子的摩尔比为1:11.5，物料W2中铵根离子与铝离子的摩尔比为1:7.5，焙烧温度为550℃，得到球形氧化铝载体S-2，载体性质见表1。
实施例3
同实施例1，只是物料W1中铵根离子与铝离子的摩尔比为1:14.5，物料W2中铵根离子与铝离子的摩尔比为1:4.5，焙烧温度为750℃，得到球形氧化铝载体S-3，载体性质见表1。
实施例4
同实施例1，只是物料W1中铵根离子与铝离子的摩尔比为1:10，物料W2中铵根离子与铝离子的摩尔比为1:9.5，焙烧温度为700℃，得到球形氧化铝载体S-4，载体性质见表1。
对比例1
同实施例1，只是物料W1和物料W2中均未加入氯化铵，制得对比球形氧化铝载体S-5，载体性质见表1。
对比例2
同实施例1，只是物料W1中未加入氯化铵，制得对比球形氧化铝载体S-6，载体性质见表1。
对比例3
同实施例1，只是物料W2中未加入氯化铵，制得对比球形氧化铝载体S-7，载体性质见表1。
对比例4
同实施例1，只是物料W1和W2中氯化铵换成相同摩尔数的氟化铵，制得对比球形氧化铝载体S-8，载体性质见表1。
对比例5
同实施例1，只是物料W1和W2中氯化铵换成相同摩尔数的柠檬酸铵，制得对比球形氧化铝载体S-9，载体性质见表1。
表1 载体的性质
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 | |
| 氧化铝载体 | S1 | S2 | S3 | S4 | S5 | S6 | S7 | S8 | S9 |
| 比表面积，m2/g | 254 | 273 | 221 | 234 | 263 | 269 | 258 | 187 | 262 |
| 孔容，mL/g | 0.96 | 0.99 | 0.92 | 0.93 | 0.97 | 0.96 | 0.95 | 0.84 | 0.96 |
| 孔分布，v% | |||||||||
| 10-20nm，% | 48 | 61 | 56 | 53 | 37 | 41 | 45 | 46 | 35 |
| 30-60nm，% | 13 | 15 | 17 | 15 | 7 | 12 | 9 | 12 | 7 |
从表1可以看出，采用本发明方法制备的氧化铝载体中10-20nm及30-60nm孔道含量较高。而滚球时拟薄水铝石中未加入氯化铵（对比例1），或拟薄水铝石A中未加入氯化铵（对比例2），或拟薄水铝石B中未加入氯化铵（对比例3）制得的氧化铝载体中10-20nm及30-60nm孔道含量低于实施例。成型时加入相同摩尔数的氟化铵时虽然可以起到扩充孔道的效果，但载体比表面积和孔容大幅降低。成型时加入相同摩尔数的柠檬酸铵时使载体孔径变小。
加氢脱金属催化剂Cat1-Cat9的制备：
将实施例1-4所得的氧化铝载体（S1、S2、S3、S4）和对比例1-5所得的氧化铝载体（S5、S6、S7、S8、S9），分别制备得到加氢脱金属催化剂Cat1-Cat9，
具体方法如下：
称取实施例1-4和对比例1-5所制备的氧化铝载体各150克，采用等体积喷淋浸渍法浸渍 Mo-Ni-P浸渍液（按最终催化剂中含MoO3 8.7wt%，NiO 2.8wt%），120℃烘干，再在550℃温度下焙烧5小时，相应得到加氢脱金属催化剂Cat1-Cat9。
催化性能评价：
将上述制备得到的加氢脱金属催化剂Cat1-Cat9进行催化性能评价，评价方法如下：
表2所列渣油为原料，在固定床渣油加氢反应装置上评价Cat1-Cat9的催化性能，反应温度为380℃，氢分压为13MPa，液时体积空速为1.0小时-1，氢油体积比为1000，反应2500小时后测定生成油中各杂质的含量，计算杂质脱除率，评价结果见表3。
表 2 原料油性质
| 项目 | |
| 密度（20℃），g/cm3 | 0.98 |
| S，wt% | 3.6 |
| N，wt% | 0.31 |
| Ni，µg/g | 51.4 |
| V，µg/g | 81.2 |
表 3 催化剂加氢性能对比
| 催化剂编号 | Cat1 | Cat2 | Cat3 | Cat4 | Cat5 | Cat6 | Cat7 | Cat8 | Cat9 |
| 脱V+Ni率，wt% | 68.5 | 72.1 | 70.4 | 69.8 | 50.8 | 53.6 | 54.9 | 63.5 | 51.1 |
由表3数据可以看出，与对比氧化铝载体相比，以本发明氧化铝为载体制备的催化剂具有较高的加氢脱金属活性和稳定性。
Claims (8)
1.一种球形氧化铝载体的制备方法，其特征在于包括如下内容：（1）将拟薄水铝石A与NH4Cl混合，得到物料W1；（2）将拟薄水铝石B与NH4Cl混合，得到物料W2；（3）将物料W1经滚球成型，得到球形前驱体I；（4）将物料W2与球形前驱体I混合，进行滚球成型，然后干燥、焙烧，得到球形氧化铝载体；
步骤（1）所述的拟薄水铝石A的孔容为0.6-1.2mL/g，比表面积为150-310m2/g，可几孔径为10-20nm；步骤（1）所述NH4Cl加入量以铵根计与拟薄水铝石以铝元素计的摩尔比为1:15-1:10；
步骤（2）所述的拟薄水铝石B的孔容为0.8-1.5mL/g，比表面积为180-350m2/g，可几孔径为15-30nm；步骤（2）所述NH4Cl加入量以铵根计与拟薄水铝石以铝元素计的摩尔比为1:10-1:4。
2.根据权利要求1所述的方法，其特征在于：步骤（1）所述NH4Cl加入量以铵根计与拟薄水铝石以铝元素计的摩尔比为1:12-1:10。
3.根据权利要求1所述的方法，其特征在于：步骤（2）所述NH4Cl加入量以铵根计与拟薄水铝石以铝元素计的摩尔比为1:8-1:5。
4.根据权利要求1所述的方法，其特征在于：所述的滚球成型在转盘成型机中进行，所述的转盘成型机转动操作条件为：转盘的倾角为40-70º，转盘的转速为10-30rpm；物料在转盘内的成型时间为5-30min。
5.根据权利要求1所述的方法，其特征在于：成型过程中向物料中喷入含胶溶剂的水溶液；所述的含胶溶剂的水溶液为硝酸、磷酸、草酸或醋酸的水溶液中的一种或几种混合，溶液的质量百分比浓度为1%-3%。
6.根据权利要求1所述的方法，其特征在于：步骤（4）所述的干燥时间为1-5小时，干燥温度为60℃-180℃。
7.根据权利要求1所述的方法，其特征在于：所述的焙烧温度为450-850℃，焙烧时间为2-6小时。
8.根据权利要求1所述的方法制备的球形氧化铝载体在重渣油加氢工艺中的应用，工艺条件为：反应温度370-410℃，氢分压12-18MPa，液时体积空速0.1-1.5h-1，氢油体积比500-2000：1。
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