CN115025806A - 一种抗铁污染催化裂化催化剂的制备方法 - Google Patents
一种抗铁污染催化裂化催化剂的制备方法 Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 19
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims description 20
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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 claims description 16
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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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
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- B01J2229/10—After treatment, characterised by the effect to be obtained
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
本发明公开了一种抗铁污染催化裂化催化剂的制备方法。该方法是通过对高岭土扩孔改性来提高催化剂的基质比表面和孔体积,同时在催化剂颗粒表面富铝以及锌改性来提高催化剂的抗铁污染能力。该催化剂在较高铁负载量下表现出较好的抗铁污染能力和优异的产品选择性,从而为加工高铁含量原油提供了一种方便可行的解决方案。
Description
技术领域
本发明涉及催化剂技术领域,具体涉及一种抗铁污染催化裂化催化剂的制备方法。
背景技术
目前,催化裂化作为原油二次加工的主要手段在石油炼制领域占有非常重要的地位,而这其中催化裂化催化剂的性能是关键性因素,它直接影响着产物分布。随着原油重质化和劣质化日益加剧,原料中的金属含量也随之增加,主要的金属元素除了钒和镍,还有铁、钙、钠、铜等。因此,对催化剂的抗金属污染性能提出了更高的要求。目前对于抗镍钒污染的相关研究很多,而对铁的较少,对于铁的中毒机理总结起来有两种合理的解释,第一种解释:铁与镍、钒等其他金属类似,铁主要存在于原料的大分子烃中,原料大分子组分在基质上进行预裂化反应的过程中,铁不断沉积在颗粒外表面,由于其迁移活性较弱而逐渐在颗粒外表面富集,最终导致基质孔道堵塞,活性中心可接近性下降,催化剂的重油转化能力降低,目标产品收率变差;第二种解释:基质孔道堵塞不止因为铁的物理沉积,还因为铁能与基质中的硅、钙、钠等形成低熔点共熔物,在熔融过程中,催化剂颗粒表面会呈现玻璃状,温度降低时则形成瘤状凸起,表面会形成1-3μm的致密壳层,从而影响油气分子的内扩散传质,因而大大降低活性中心的数量,严重时还会影响催化剂在装置内的流化。
基于上述破坏机理,想提高抗铁污染性能,一方面是增加催化剂基质组分的比表面积和孔体积,分散低熔点共熔物,减少共熔物对催化剂孔道的堵塞;另一方面是提高催化剂基质中的氧化铝的含量,使铁氧化物尽可能多地沉积在氧化铝表面减少低熔点共熔物的生成。
目前有关制备抗铁污染催化剂的专利技术很少,因此急需一种切实可行的催化剂制备工艺技术,为加工高铁原油提供一种切实可行的催化剂使用方案。
CN107303507A公开了一种含磷和硅氧化铝的制备方法,该方法制备的氧化铝载体保持拟薄水铝石高比表面积和大孔体积的特点,并且氧化铝载体的酸量可以用磷和硅的含量在较大范围内简单地调节,使载体可以用于多个领域,在催化裂化催化剂制备过程中加入本发明氧化铝,可提高催化剂的重油转化能力,提高目标产品收率。
CN102188963A公开了一种高岭土的改性方法,以高岭土为原料,先将高岭土进行高温焙烧处理,而后将高温焙烧过的高岭土与外加铝源和酸性溶液搅拌均匀后制得混合浆液,在一定条件下反应后不需过滤即可直接作为制备催化裂化催化剂的原料。这种改性高岭土具有发达的中大孔孔体积和一定的活性,同时含这种改性高岭土的浆液还具有一定的粘结性能,采用含这种改性高岭土浆液制备的催化剂表现出更强的抗重金属能力。
CN109692694A公开了一种大孔高岭石及其制备和应用,所述大孔高岭石含稀土,平均孔直径为2-50nm,孔直径为10-50nm的孔的孔容占总孔容的80%以上。所述大孔高岭石的制备方法,包括如下步骤:将高岭土进行第一焙烧,将第一焙烧后的高岭土及第一酸性溶液、任选的稀土化合物形成混合物,进行第一处理,然后进行第二焙烧,再与第二酸性溶液及扩孔剂、任选的稀土化合物混合,进行第二处理,过滤、干燥,得到大孔高岭石,其中第一处理和第二处理的至少一个步骤引入稀土化合物。所述大孔高岭石裂化活性高,用于催化剂裂化催化剂代替粘土,在稀土含量相当的前提下,焦炭选择性较好,抗重金属污染能力强,汽油产率高。
发明内容:
为了提高催化剂的抗铁污染能力,实现稳定、高效加工高铁原油的目的,本发明公开了一种抗铁污染催化裂化催化剂的制备方法,该方法的具体步骤如下:
(1)高岭土与磷铝胶混合打浆,控制固含量≥50%,搅拌时间≥6小时;
(2)铝溶胶中加入聚乙二醇,搅拌待用;
(3)拟薄水铝石加水打浆,加入硼酸预酸化;
(4)REY分子筛加水打浆,搅拌待用;
(5)将(1)(2)(3)(4)中的浆液并流混合均习,加入盐酸,控制pH在2.2-3.0之间,喷雾造粒、焙烧、洗涤干燥后即得成品。
步骤(1)中,磷铝胶加入比例以P2O5计占成品干基的5-10wt%。
步骤(1)中,磷铝胶的组成为P2O5与Al2O3摩尔比为4.5-10。
步骤(2)中,聚乙二醇的分子量为1000~2000g/mol,加入比例占以Al2O3计的铝溶液的0.001~0.01wt%。
步骤(3)中,硼酸的加入比例,以H3BO3计占以Al2O3计的拟薄水铝石的0.1-0.3wt%。
步骤(5)中,在喷雾塔底部连接焙烧炉的管线上增加开口,以实现连续加入氢氧化锌的目的,其中氢氧化锌的加入比例以ZnO计,占成品干基的0.1-0.5wt%。本发明的创新点或优势为:
(1)高岭土先与磷铝胶打浆,磷铝胶的组成为P2O5与Al2O3摩尔比为4.5-10,除了可作粘结剂,过量的磷酸使得浆液的pH值较低,通过控制打浆固含量与搅拌时间,搅拌的剪切摩擦使浆液温度升高,两者共同作用,使得高岭土的一小部分氧化铝溶解进入浆液,孔道变得疏通与宽阔,增加了高岭土的比表面积,可有效降低铁污染的堵孔作用。
(2)铝溶胶中加入聚乙二醇,提高胶团的分散与表面张力,浆液在喷雾干燥过程中更快的收缩成球形,而且使得铝溶胶更多地分散在颗粒外表面,实现了表面富铝的目的。
(3)硼酸预酸化拟薄水铝石,利用硼酸熔点169℃(分解),沸点300℃的特性,在焙烧时会形成一定比例的孔穴,改善了催化剂的扩散性能。
(4)氢氧化锌与催化剂颗粒一并进入焙烧炉,氢氧化锌在125℃分解成氧化锌与水,氧化锌吸附在催化剂颗粒的表面,其可与铁形成高熔点物质起到固铁的目的,减少铁的毒性。
(5)磷铝胶中过量的磷酸与各物质接触,形成了磷羟基,增加了催化剂的酸性中心数,提高了催化剂的裂化能力。
通过以上技术手段制备出的催化剂,相比于常规方式制备的催化剂,具有更高的中大孔比表面积和更多的中强酸中心数量,在应用时,具有优良的抗铁污染能力,能够降低干气、焦炭等低附加值产物的产生,从而提高了炼油的经济效益。
具体实施方式:
下面将结合实施例对本发明进一步说明,需要说明的是以下所述的实施例仅仅是本发明的一部分实施例,并不意味着是对本发明范围的限制。
本发明实施例中所用原料规格:
高岭土:工业级,中国高岭土有限公司,灼减25.5%;
铝溶胶:自产Al2O3含量21.5wt%;
聚乙二醇:分析纯,分子量1000-2000;
拟薄水铝石:工业级,中国铝业股份山东分公司,灼减29.5wt%;
REY分子筛:自产,RE2O3含量7.5-9.0wt%、灼减25.0wt%;
磷铝胶:自制,P2O5+Al2O3含量40wt%;
盐酸:分析纯;
氢氧化锌:分析纯。
实施例1
(1)称取700克高岭土、160克磷铝胶(磷铝比4.5),加水600克,控制浆液固含量≥50%,混合打浆16小时,浆液温度控制在80-90℃之间;
(2)称取200克铝溶胶、0.007克聚乙二醇,并将聚乙二醇加入铝溶胶中搅拌均匀待用;
(3)称取360克拟薄水铝石,加水350克打浆,加入0.5克的硼酸;
(4)600克REY分子筛加水600克打浆待用;
(5)将(1)(2)(3)(4)的浆液并流加入混合打浆,并加入盐酸进行酸化,控制pH值在2.2-3.0之间,喷雾干燥,焙烧时加入氢氧化锌3克,洗涤干燥、样品标为Cat-1。
实施例2
(1)称取700克高岭土、200克磷铝胶(磷铝比4.5),加水550克,控制浆液固含量≥50%,混合打浆16小时,浆液温度控制在80-90℃之间;
(2)称取200克铝溶胶、0.007克聚乙二醇,并将聚乙二醇加入铝溶胶中搅拌均匀待用;
(3)称取360克拟薄水铝石,加水350克打浆,加入0.5克的硼酸;
(4)600克REY分子筛加水600克打浆待用;
(5)将(1)(2)(3)(4)的浆液并流加入混合打浆,并加入盐酸进行酸化,控制pH值在2.2-3.0之间,喷雾干燥,焙烧时加入氢氧化锌3克,洗涤干燥、样品标为Cat-2。
实施例3
(1)称取700克高岭土、250克磷铝胶(磷铝比4.5),加水500克,控制浆液固含量≥50%,混合打浆16小时,浆液温度控制在80-90℃之间;
(2)称取200克铝溶胶、0.007克聚乙二醇,并将聚乙二醇加入铝溶胶中搅拌均匀待用;
(3)称取360克拟薄水铝石,加水350克打浆,加入0.5克的硼酸;
(4)600克REY分子筛加水600克打浆待用;
(5)将(1)(2)(3)(4)的浆液并流加入混合打浆,并加入盐酸进行酸化,控制pH值在2.2-3.0之间,喷雾干燥,焙烧时加入氢氧化锌5克,洗涤干燥、样品标为Cat-3。
实施例4
(1)称取700克高岭土、160克磷铝胶(磷铝比6.0),加水500克,控制浆液固含量≥50%,混合打浆16小时,浆液温度控制在80-90℃之间;
(2)称取200克铝溶胶、0.007克聚乙二醇,并将聚乙二醇加入铝溶胶中搅拌均匀待用;
(3)称取360克拟薄水铝石,加水350克打浆,加入0.8克的硼酸;
(4)600克REY分子筛加水600克打浆待用;
(5)将(1)(2)(3)(4)的浆液并流加入混合打浆,并加入盐酸进行酸化,控制pH值在2.2-3.0之间,喷雾干燥,焙烧时加入氢氧化锌3克,洗涤干燥、样品标为Cat-4。
实施例5
(1)称取700克高岭土、250克磷铝胶(磷铝比6.0),加水500克,控制浆液固含量≥50%,混合打浆16小时,浆液温度控制在80-90℃之间;
(2)称取200克铝溶胶、0.007克聚乙二醇,并将聚乙二醇加入铝溶胶中搅拌均匀待用;
(3)称取360克拟薄水铝石,加水350克打浆,加入0.5克的硼酸;
(4)600克REY分子筛加水600克打浆待用;
(5)将(1)(2)(3)(4)的浆液并流加入混合打浆,并加入盐酸进行酸化,控制pH值在2.2-3.0之间,喷雾干燥,焙烧时加入氢氧化锌5克,洗涤干燥、样品标为Cat-5。
对比例
(1)称取840克高岭土、200克铝溶胶,加水1600克,混合打浆16小时;
(2)称取600克REY分子筛加水1000克打浆待用;
(3)称取360克拟薄水铝石;
(4)将(2)的分子筛浆液加入(1)中进行混合打浆,并将(3)称取的拟薄水铝石倒入混合浆液中进行搅拌均匀,并进行补水,保持固含量在35%左右,加入盐酸进行酸化,控制pH值在2.2-3.0之间,喷雾造粒、洗涤、干燥,样品标为Cat-DB。
对上述制备的催化剂理化指标进行分析测试,其结果如表1所示:
表1催化剂理化数据
从表1可以看出,利用本方法制备的催化剂比表面要比正常催化剂高出20-40m2/g,并且这部分主要是基质比表面增加的结果,微孔比表面变化很小。
采用环烷酸铁饱和浸渍法对上述催化剂进行有机铁污染浸渍,铁目标上量为12000ppm,浸渍后的样品再用吊篮水热老化装置进行水热老化失活处理,水热老化条件760℃、100%水蒸气下老化处理10h。最后将处理好的催化剂样品分别置于ACE-AP中进行性能评价,催化剂装填量9克,反应温度527℃,剂油比6。评价所用原料油的组成如表2所示,ACE评价结果如表3所示。
表2原料油基本性质
表3催化剂评价结果
从表3评价结果可以看出,实施例1-5催化剂的转化率要明显高于对比例0.4-1.3个百分点,表现出较好的抗铁污染能力和优异的产品选择性。
Claims (6)
1.一种抗铁污染催化裂化催化剂的制备方法,其具体步骤如下:
(1)高岭土与磷铝胶混合打浆,控制固含量≥50%,搅拌时间≥6小时;
(2)铝溶胶中加入聚乙二醇,搅拌均匀待用;
(3)拟薄水铝石加水打浆,并加入硼酸预酸化;
(4)REY分子筛加水打浆,搅拌均匀待用;
(5)将(1)(2)(3)(4)中的浆液并流加入打浆桶内搅拌均匀,再加入盐酸进行酸化,控制pH在2.2-3.0之间,最后喷雾造粒、焙烧、洗涤干燥后即得成品。
2.根据权利要求书1所述的制备方法,其特征在于:步骤(1)中,磷铝胶的加入比例以P2O5计占成品干基的5-10wt%。
3.根据权利要求书1所述的制备方法,其特征在于:步骤(1)中,磷铝胶的组成为P2O5与Al2O3摩尔比为4.5-10。
4.根据权利要求书1所述的制备方法,其特征在于:步骤(2)中聚乙二醇的分子量为1000-2000g/mol,加入比例占以Al2O3计的铝溶胶的0.001~0.01wt%。
5.根据权利要求书1所述的制备方法,其特征在于:步骤(3)中硼酸的加入比例以H3BO3计占以Al2O3计的拟薄水铝石的0.1-0.3wt%。
6.根据权利要求书1所述的制备方法,其特征在于:步骤(5)中在喷雾塔底部连接焙烧炉的管线上增加开口,以实现连续加入氢氧化锌的目的,其中氢氧化锌的加入比例以ZnO计,占成品干基的0.1-0.5wt%。
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