CN115069296A - 一种增产优质针状焦原料的催化裂化催化剂的制备方法 - Google Patents
一种增产优质针状焦原料的催化裂化催化剂的制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 42
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 239000002808 molecular sieve Substances 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 12
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- 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 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
本发明公开了一种增产优质针状焦原料的催化裂化催化剂的制备方法,通过pH摇摆法制备富含磷羟基的硅铝基质材料,该基质材料具有适宜的酸量和孔径分布,并添加了有利于芳构化和抗金属污染的活性组分,能够增产优质的可用来制备针状焦的油浆和低碳烯烃,为炼厂增加经济效益。
Description
技术领域
本发明属于催化剂制备技术领域,具体涉及一种增产优质针状焦原料的催化裂化催化剂的制备方法
背景技术
随着原油的持续开采,其性质变差,不利于生产轻质油品,影响炼厂经济效益,尤其是部分炼厂回炼油浆量很大,影响装置安全生产,急需新的对策。
针状焦是一种高性能的碳材料,其表面线条清晰,显微镜下可观察到纤维结构,具有热膨胀系数小,石墨化程度高,耐热耐腐蚀,各向异性程度高等特点,广泛应用于高功率(HP)和超高功率(UHP)石墨电极,特殊功能材料及其复合碳材料等领域。、
针状焦根据生产原料不同可分为煤系针状焦和石油针状焦两种类型,一般来说,石油针状焦的性能更优越,石墨化程度更高,生产的电极材料的导电能力更强,石油针状焦的原料要求为短侧链多环芳烃含量高,胶质沥青质含量低,硫、氮和金属含量低,粘度低,分子量分布范围窄。催化油浆富含短侧链稠环芳烃是油系针状焦的优良原料之一。
CN1180056C一种催化裂化澄清油生产针状焦的方法,是先用润滑油抽出液萃取催化裂化澄清油,然后将脱除催化剂粉末的澄清油经延迟焦化生产针状焦,含有催化剂粉末的抽出油与渣油原料一起生产普通石油焦,或作为燃料油使用。
CN114369474A本发明涉及针状焦生产领域,具体涉及一种油基针状焦生产装置及生产工艺。
CN113817497A本发明公开了一种油系针状焦原料深减压预处理系统,包括加热炉,减压塔,减压汽提塔,一线油出系统,二线油出系统,三线油出系统,顶污油出系统,沥青油出系统,油浆换热系统,实现了油浆的多级分离,组分更加简单,有利于进行后续的焦化处理,得到质量更高的针状焦产品。
当然催化油浆的成分复杂,馏程范围宽,需要进行预处理,常用的方法为减压蒸馏工艺,除去固体颗粒和油渣质后,抽提出芳烃组成,作为生产针状焦的原料。因此需要一种合适的催化剂,有较佳的芳构化能力,适度的裂化能力,较好的抗金属污染能力,较佳的磨损性能减少细粉的产生。
发明内容
针对现有技术存在的一些问题,本发明的目的是提供一种催化剂的制备方法,通过pH摇摆法制备富含磷羟基的硅铝基质材料,该基质材料具有适宜的酸量和孔径分布,并添加了有利于芳构化和抗金属污染的活性组分,能够增产优质的可用来制备针状焦的油浆和低碳烯烃,为炼厂增加经济效益。
本发明所述制备方法其步骤具体如下:
(1)铝溶胶与磷酸溶液混合均匀,加入一定量的磷酸二氢铵,整个过程溶液温度应小于20℃,记做浆液A;
(2)向水玻璃、偏铝酸钠混合溶液中加入磷酸,控制加入速度,加完后恒温陈化一段时间,记做浆液B;
(3)将浆液A与B按一定的比例混合,继续加入磷酸至pH值小于4.0,搅拌均匀后加入氨水至浆液pH值7.5±0.5,过滤,洗涤;
(4)将(3)中滤饼重新打浆,加入ZSM-5分子筛、Y型分子筛和轻质氧化镁,磨细后酸化,喷雾造粒,洗涤烘干后即得标题物。
步骤(1)中铝溶胶、磷酸和磷酸二氢铵加入比例分别以Al2O3、P2O5、NH4(H2PO4)的质量计为1:0.05-0.09:0.003-0.03。
步骤(2)中水玻璃、偏铝酸钠和磷酸加入比例分别以SiO2、Al2O3和P2O5的质量计为1:0.3-0.9:0.5-1。
步骤(3)中浆液A与B加入比例以氧化物计为2-5:1。
步骤(4)中的ZSM-5为碱处理和锌改性,硅铝比20-60,氧化锌含量1-2wt%,改性后介孔比表面占总比表面的20-30%。
步骤(4)中Y型分子筛氧化稀土含量为2-4wt%,晶胞常数24.55-24.60。
步骤(4)中Y+ZSM-5的加入比例占标题物干基的30-45wt%,氧化镁的加入比例占标题物干基的1-3wt%。。
本发明制备的催化剂用于增产优质针状焦原料的有益之处为:
(1)富含磷羟基的硅铝材料,可通过调整磷、铝和硅三者的比例,调变比表面积、孔径分布和酸量,以实现控制原料油裂解深度的目的;磷羟基属于中强酸,可实现多环芳烃侧链的断链,又不至于裂化过度生成过多的汽油和柴油。
(2)使用碱处理和锌改性的ZSM-5和低稀土Y型分子筛,前者是为了多产低碳烯烃,提高芳构化能力;后者也是为了控制氢转移活性,降低焦炭产率。
(3)酸化前添加一定比例的轻质氧化镁,可以起到抗金属污染的目的,延长催化剂的寿命。
(4)通过调整A和B的比例,在酸化时可以控制硅铝材料酸化难易度,让分子筛更好的分散和结合,保证其可接近性,也能保证催化剂的磨损性能,减少超细粉的产生,降低油浆中灰分含量。
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。
所用原材料均为工业品,取自青岛惠城环保科技股份有限公司生产车间。
实施例1
(1)将2000克铝溶胶(Al2O3=22.0wt%)与48.8克75wt%磷酸溶液混合均匀,加入3.52克的磷酸二氢铵,整个过程溶液温度小于20℃,记做浆液A;
(2)向1000ml水玻璃(SiO2=60g/L)、300ml偏铝酸钠(Al2O3=100g/L)混合溶液中加入66.6克75wt%磷酸,控制加入速度,加完后恒温陈化一段时间,记做浆液B;
(3)将浆液A与B按照3:1的比例混合,继续加入磷酸至pH值小于4.0,搅拌均匀后加入氨水至浆液pH值7.8,过滤,洗涤;
(4)将(3)中滤饼重新打浆,加入224.5gZSM-5分子筛、179.6gY型分子筛和13.47g轻质氧化镁,磨细后酸化,喷雾造粒,洗涤烘干后记做CAT-1。
实施例2
(1)将2000克铝溶胶(Al2O3=22.0wt%)与63.6克75wt%磷酸溶液混合均匀,加入4.4克的磷酸二氢铵,整个过程溶液温度小于20℃,记做浆液A;
(2)向1000ml水玻璃(SiO2=60g/L)、180ml偏铝酸钠(Al2O3=100g/L)混合溶液中加入80.0克75wt%磷酸,控制加入速度,加完后恒温陈化一段时间,记做浆液B;
(3)将浆液A与B按照4:1的比例混合,继续加入磷酸至pH值小于4.0,搅拌均匀后加入氨水至浆液pH值7.8,过滤,洗涤;
(4)将(3)中滤饼重新打浆,加入230.0gZSM-5分子筛、92.0gY型分子筛和27.6g轻质氧化镁,磨细后酸化,喷雾造粒,洗涤烘干后记做CAT-2。
实施例3
(1)将2000克铝溶胶(Al2O3=22.0wt%)与78.2克75wt%磷酸溶液混合均匀,加入8.8克的磷酸二氢铵,整个过程溶液温度小于20℃,记做浆液A;
(2)向1000ml水玻璃(SiO2=60g/L)、360ml偏铝酸钠(Al2O3=100g/L)混合溶液中加入111.1克75wt%磷酸,控制加入速度,加完后恒温陈化一段时间,记做浆液B;
(3)将浆液A与B按照2:1的比例混合,继续加入磷酸至pH值小于4.0,搅拌均匀后加入氨水至浆液pH值7.8,过滤,洗涤;
(4)将(3)中滤饼重新打浆,加入113.3gZSM-5分子筛、188.8gY型分子筛和15.1g轻质氧化镁,磨细后酸化,喷雾造粒,洗涤烘干后记做CAT-3。
实施例4
(1)将2000克铝溶胶(Al2O3=22.0wt%)与88克75wt%磷酸溶液混合均匀,加入13.2克的磷酸二氢铵,整个过程溶液温度小于20℃,记做浆液A;
(2)向1000ml水玻璃(SiO2=60g/L)、500ml偏铝酸钠(Al2O3=100g/L)混合溶液中加入133.3克75wt%磷酸,控制加入速度,加完后恒温陈化一段时间,记做浆液B;
(3)将浆液A与B按照5:1的比例混合,继续加入磷酸至pH值小于4.0,搅拌均匀后加入氨水至浆液pH值7.8,过滤,洗涤;
(4)将(3)中滤饼重新打浆,加入199.4gZSM-5分子筛、199.4gY型分子筛和9.97g轻质氧化镁,磨细后酸化,喷雾造粒,洗涤烘干后记做CAT-4。
制备好的催化剂样品分别置于RU-2000提升管评价装置进行性能评价,评价前需将催化剂预先进行800℃,100%H2O,17小时的水热老化处理,催化剂装填量10000克,反应温度510℃。评价所用原料油的组成如表1所示。
表1原料油基本性质
操作平稳后,取一小时的平均数据,反应收集的液体产物进行分馏,获得汽柴油和油浆,并对油浆进行相关指标的分析,数据如下:
从上述评价数据可以看出,本实施例制备的催化剂具有优异的反应性能,可以获得理想的产物分布,并根据目的产物易于调整配方,为炼厂增收提供一种可行的方案。
Claims (6)
1.一种增产优质针状焦原料的催化裂化催化剂的制备方法,其具体步骤如下:
(1)铝溶胶与磷酸溶液混合均匀,加入一定量的磷酸二氢铵,整个过程溶液温度应小于20℃,记做浆液A;
(2)向水玻璃、偏铝酸钠混合溶液中加入磷酸,控制加入速度,加完后恒温陈化一段时间,记做浆液B;
(3)将浆液A与B按一定的比例混合,继续加入磷酸至pH值小于4.0,搅拌均匀后加入氨水至浆液pH值7.5±0.5,过滤,洗涤;
(4)将(3)中滤饼重新打浆,加入ZSM-5分子筛、Y型分子筛和轻质氧化镁,磨细后酸化,喷雾造粒,洗涤烘干后即得标题物。
2.根据权利要求1所述的制备方法,其特征在于步骤(1)中铝溶胶、磷酸和磷酸二氢铵加入比例分别以Al2O3、P2O5、NH4H2PO4的质量计为1:0.05-0.09:0.003-0.03。
3.根据权利要求1所述的制备方法,其特征在于步骤(2)中水玻璃、偏铝酸钠和磷酸加入比例分别以SiO2、Al2O3和P2O5的质量计为1:0.3-0.9:0.5-1。
4.根据权利要求1所述的制备方法,其特征在于步骤(3)中浆液A与B加入比例以氧化物计为2-5:1。
5.根据权利要求1所述的制备方法,其特征在于步骤(4)中的ZSM-5为碱处理和锌改性过,硅铝比20-60,氧化锌含量1-2wt%,改性后介孔比表面占总比表面的20-30%。
6.根据权利要求1所述的制备方法,其特征在于步骤(4)中Y型分子筛氧化稀土含量为2-4wt%,晶胞常数24.55-24.60埃。
根据权利要求1所述的制备方法,其特征在于步骤(4)中Y+ZSM-5的加入比例占标题物干基的30-45wt%,氧化镁的加入比例占标题物干基的1-3wt%。
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