CN114749205A - 一种用于原油直接裂解制低碳烯烃催化剂的制备方法 - Google Patents
一种用于原油直接裂解制低碳烯烃催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000005336 cracking Methods 0.000 title claims abstract description 12
- 239000010779 crude oil Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims description 41
- 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 41
- 239000002002 slurry Substances 0.000 claims description 37
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 23
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 9
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- 239000001164 aluminium sulphate Substances 0.000 claims description 7
- 235000011128 aluminium sulphate Nutrition 0.000 claims description 7
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 7
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
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- 238000006257 total synthesis reaction Methods 0.000 abstract description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 13
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
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- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
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- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
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- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
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- 238000004230 steam cracking Methods 0.000 description 1
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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
- B01J29/40—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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- 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
- B01J37/0063—Granulating
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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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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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
本发明公开了一种用于原油直接裂解制低碳烯烃催化剂的制备方法,该催化剂采用全合成技术并结合核壳制备技术,解决了ZSM‑5晶化母液处理问题,又能将ZSM‑5晶体均匀分散于具有较大孔径和比表面积的硅铝载体上,再结合后合成的高硅铝比ZSM‑5,在催化剂颗粒上形成了酸量的梯度分布,更加有利于低碳烯烃的形成。
Description
技术领域
本发明涉及催化剂技术领域,具体涉及一种原油直接裂解制低碳烯烃催化剂的制备方法。
背景技术
低碳烯烃通常指碳四及碳四以下的不饱和碳氢化合物的总称,包括乙烯、丙烯、丁烯等,是不可或缺的化工原料,尤其是随我国经济的发展这些有机化工原料的需求量逐年增长,而产量不能满足日益增长的需求,因此有效提高低碳烯烃产量成为研发的热点之一。
目前,生产低碳烯烃的主要方式有蒸汽裂解、催化裂化丙烷脱氢、MTO催化重整等,生产过程中均存在较高的CO2排放问题,在碳中和战略目标影响下其发展收到极大的限制,而随着新能源汽车的推广,成品油的生产收益逐年递减,如何实现炼油厂利益最大化成为迫切的需求,而催化裂解制低碳烯烃所需温度相对较低,能耗低、原料适用性广,是未来生产低碳烯烃的重要途径。
原油四组分是指饱和分、芳香分、胶质和沥青质,包含有沸点超过590℃的高分子量非挥发性组分,而催化剂性质决定裂解性能以及产物分布,石油裂解催化剂的活性组分主要是ZSM-5分子筛,其孔口直径约为0.53nm,重油大分子难以进入ZSM-5孔道进行反应,较大的反应产物也不易从孔道中扩散出去。此外,反应过程中ZSM-5存在水热稳定性差、易积碳失活的问题。
针对以上问题学者们开展了大量研究,发现可以通过调控催化剂的孔径制备多级孔结构的分子筛催化剂或将ZSM-5与大孔结构的Y分子筛复配改善其性能。
专利CN102757069A一种分子筛合成时所产生的母液重新回用的方法,是将母液中的游离硅用酸法沉淀以生成硅胶湿滤饼,再和其他硅源及铝源混合,实现无胺法合成ZSM-5分子筛。这种回用方法,操作简单,成本低廉,晶化时间缩短,污染物排放量降低。所产ZSM-5分子筛较常规ZSM-5分子筛晶粒小,相对结晶度高。
专利CN103708496A公开了一种HZSM-5@silicalite-1核壳结构分子筛及其制备方法与应用。该方法是以HZSM-5分子筛为核,以全硅silicalite-1分子筛为壳,形成的壳层均匀致密,厚度为10~70nm。该发明制备的HZSM-5@silicalite-1核壳结构分子筛用于溴甲烷甲基化甲苯制备对二甲苯时具有优越的催化活性,对位选择性和稳定性。
专利CN108658093A公开一种多级孔ZSM-5分子筛的制备方法,该方法是通过在硅源、铝源、有机结构导向剂和去离子水的合成体系中,添加适量阳离子型表面活性剂十六烷基三甲基溴化铵作为软模板剂,充分搅拌混合均匀形成分子筛合成溶胶凝胶,然后将上述凝胶烘干得到干胶,再利用干胶转化法制备多级孔ZSM-5分子筛。
专利CN108745410B公开一种含磷的多级孔ZSM-5/Y复合分子筛的制备方法,该方法是将碱、有机模板剂和去离子水混合成为溶液,再加入NaY分子筛,加入硅源和硼源,得到混合溶胶晶化,回收晶化产品后脱除模板剂,得到NaZSM-5/Y复合分子筛;然后在铵盐溶液中进行铵离子交换脱除Na离子,得到NH4-ZSM-5/Y复合分子筛;再脱除骨架中硼元素,用磷化物浸渍,得到含磷的ZSM-5/Y复合分子筛。
专利CN113385223A公开一种直接催化裂解原油增产低碳烯烃的催化剂及其制备方法,该方法制备的催化剂包含5-20%Y型分子筛,20-50%的磷和锆改性ZSM-5分子筛,10-40%载体,5-25%粘结剂,该催化剂的特点在于以磷和锆共改性ZSM-5分子筛调控催化剂酸量和催化剂孔道分布,利于反应物在催化剂的扩散和目标产物的生成。该催化剂用于原油直接催化裂解过程中能抑制二次反应的发生、提高产物中低碳烯烃的收率。
原油的裂解工艺一般均在较高的反应温度下,热裂化反应比较激烈。为了防止过度的热裂化反应,就需要原油与催化剂接触时,能够快速的汽化和分散,催化剂应具有合适的比表面积、孔径和酸性,避免过裂化。另外,反应以热裂化为主,就需要控制氢转移反应和裂化深度。因此,选择合适的硅铝比ZSM-5比Y型分子筛更适合,ZSM-5分子筛的孔道是反应的场所,也是避免过度裂化和烯烃饱和的场所,其协同作用有利于低碳烯烃的形成与保存。
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。该催化剂采用全合成技术并结合核壳制备技术,将ZSM-5分子筛晶化后的浆液与硅铝源混合后喷雾造粒,既可以解决ZSM-5生产母液处理难题,又能将ZSM-5活性组分均匀分散于硅铝载体上,而且形成的硅铝载体具有大孔径和大比表面积的特点,有利于原油大分子的扩散与预裂化深度控制,再晶化时形成的高硅铝比ZSM-5分子筛大部分分布在颗粒的外表面或浅处,形成了酸密度的梯度分布,在原油裂解中形成了接力和协同效应,更加有利于低碳烯烃的形成。
其合成步骤如下:
(1)ZSM-5分子筛晶化完成后的浆液与硫酸铝溶液、酸性硅溶胶并流混合,快速搅拌均匀,过滤后喷雾干燥造粒、焙烧、洗涤、过滤,获得的颗粒物记作A。
(2)将N-甲基二乙醇胺模板剂加入硫酸铝溶液中,搅拌均匀,将该浆液记作B。
(3)将A用水打浆,水玻璃与B并流加入浆液A中,混合均匀后升温晶化。
(4)晶化完毕,过滤、洗涤、干燥后得到标题物。
步骤(1)中ZSM-5分子筛硅铝比为60-120,硫酸铝以氧化铝计,硅溶胶以氧化硅计,其与ZSM-5分子筛三者的质量比为(0.12-0.30):(0.06-0.10):1;
步骤(1)中焙烧温度为400-450℃,洗涤后要求SO4 2-≤5.0wt%;
步骤(2)中N-甲基二乙醇胺加入比例与以氧化铝计的硫酸铝的质量比为(0.001-0.01):1;
步骤(3)中,各物料加入比例以摩尔计为ZSM-5晶化后的浆液(以ZSM-5中的Al2O3计):水玻璃(以SiO2计):硫酸铝(以Al2O3计):模板剂:H2O=(0.8-4.0):(250-500):1:(0.05-0.25):(800-1000);
1.步骤(4)中,洗涤液中应含有硫酸铵,洗涤后催化剂中的氧化纳含量应小于0.2wt%。
具体实施方式
以下对本发明的具体实施方式进行详细说明,应当理解的是,此处描述的内容仅仅用于说明和解释本发明,并不用于限制本发明。
实施例1
(1)将ZSM-5分子筛晶化完成后的浆液与硫酸铝溶液、酸性硅溶胶按照质量比为100:12:6并流混合,快速搅拌均匀,过滤后喷雾干燥造粒、焙烧、洗涤、过滤,获得的颗粒物记作A,焙烧温度为400-450℃,洗涤后要求SO4 2-≤5.0wt%;
(2)将N-甲基二乙醇胺模板剂与硫酸铝按照质量比1:100进行称重,并将模板剂倒入硫酸铝溶液中,搅拌均匀,将该浆液记作B;
(3)将A用水打浆,并将水玻璃和B并流加入A的浆液中,混合均匀后升温晶化,其中各原料组分的配比以摩尔计为ZSM-5晶化后的浆液(以ZSM-5中的Al2O3计):水玻璃(以SiO2计):硫酸铝(以Al2O3计):模板剂:H2O=1:250:1:0.2:800;
(4)晶化完毕后,将浆液过滤、洗涤、干燥后得到目标产物CAT-1。
实施例2
(1)将ZSM-5分子筛晶化完成后的浆液与硫酸铝溶液、酸性硅溶胶按照质量比为100:15:8并流混合,快速搅拌均匀,过滤后喷雾干燥造粒、焙烧、洗涤、过滤,获得的颗粒物记作A,焙烧温度为400-450℃,洗涤后要求SO4 2-≤5.0wt%;
(2)将N-甲基二乙醇胺模板剂与硫酸铝按照质量比1:250进行称重,并将模板剂倒入硫酸铝溶液中,搅拌均匀,将该浆液记作B;
(3)将A用水打浆,并将水玻璃和B并流加入A的浆液中,混合均匀后升温晶化,其中各原料组分的配比以摩尔计为ZSM-5晶化后的浆液(以ZSM-5中的Al2O3计):水玻璃(以SiO2计):硫酸铝(以Al2O3计):模板剂:H2O=2:300:1:0.2:900;
(4)晶化完毕后,将浆液过滤、洗涤、干燥后得到目标产物CAT-2。
实施例3
(1)将ZSM-5分子筛晶化完成后的浆液与硫酸铝溶液、酸性硅溶胶按照质量比为100:20:10并流混合,快速搅拌均匀,过滤后喷雾干燥造粒、焙烧、洗涤、过滤,获得的颗粒物记作A,焙烧温度为400-450℃,洗涤后要求SO4 2-≤5.0wt%;
(2)将N-甲基二乙醇胺模板剂与硫酸铝按照质量比1:500进行称重,并将模板剂倒入硫酸铝溶液中,搅拌均匀,将该浆液记作B;
(3)将A用水打浆,并将水玻璃和B并流加入A的浆液中,混合均匀后升温晶化,其中各原料组分的配比以摩尔计为ZSM-5晶化后的浆液(以ZSM-5中的Al2O3计):水玻璃(以SiO2计):硫酸铝(以Al2O3计):模板剂:H2O=2:300:1:0.25:1000;
(4)晶化完毕后,将浆液过滤、洗涤、干燥后得到目标产物CAT-3。
实施例4
(1)将ZSM-5分子筛晶化完成后的浆液与硫酸铝溶液、酸性硅溶胶按照质量比为100:20:10并流混合,快速搅拌均匀,过滤后喷雾干燥造粒、焙烧、洗涤、过滤,获得的颗粒物记作A,焙烧温度为400-450℃,洗涤后要求SO4 2-≤5.0wt%;
(2)将N-甲基二乙醇胺模板剂与硫酸铝按照质量比1:700进行称重,并将模板剂倒入硫酸铝溶液中,搅拌均匀,将该浆液记作B;
(3)将A用水打浆,并将水玻璃和B并流加入A的浆液中,混合均匀后升温晶化,其中各原料组分的配比以摩尔计为ZSM-5晶化后的浆液(以ZSM-5中的Al2O3计):水玻璃(以SiO2计):硫酸铝(以Al2O3计):模板剂:H2O=2:400:1:0.25:1000;
(4)晶化完毕后,将浆液过滤、洗涤、干燥后得到目标产物CAT-4。
实施例5
(1)将ZSM-5分子筛晶化完成后的浆液与硫酸铝溶液、酸性硅溶胶按照质量比为100:20:10并流混合,快速搅拌均匀,过滤后喷雾干燥造粒、焙烧、洗涤、过滤,获得的颗粒物记作A,焙烧温度为400-450℃,洗涤后要求SO4 2-≤5.0wt%;
(2)将N-甲基二乙醇胺模板剂与硫酸铝按照质量比1:1000进行称重,并将模板剂倒入硫酸铝溶液中,搅拌均匀,将该浆液记作B;
(3)将A用水打浆,并将水玻璃和B并流加入A的浆液中,混合均匀后升温晶化,其中各原料组分的配比以摩尔计为ZSM-5晶化后的浆液(以ZSM-5中的Al2O3计):水玻璃(以SiO2计):硫酸铝(以Al2O3计):模板剂:H2O=4:500:1:0.25:1000;
(4)晶化完毕后,将浆液过滤、洗涤、干燥后得到目标产物CAT-5。
对比例
(1)先制备一定量的磷铝胶;
(2)称取一定量的磷铝胶、高岭土、水,将三者导入不锈钢桶内进行搅拌均匀;
(3)称取一定量的ZSM-5分子筛浆液,并将分子筛浆液导入步骤(2)中的浆液中进行混合搅拌均匀,搅拌均匀后再加入一定量的硅溶胶再进行搅拌均匀;
(4)将步骤(3)的浆料进行离心喷雾干燥后得到对比剂CAT-0。
制备好的催化剂样品分别置于ACE-AP中进行性能评价,评价前需将催化剂预先进行800℃,100%H20,17小时的水热老化处理,催化剂装填量12克,反应温度620℃,剂油比20。评价所用原料油的组成如表1所示,ACE评价结果结果如表2所示。
表1原料油基本性质
表2催化剂评价结果
Claims (6)
1.一种用于原油直接裂解制低碳烯烃催化剂的制备方法,其具体步骤如下:
(1)ZSM-5分子筛晶化完成后的浆液与硫酸铝溶液、酸性硅溶胶并流混合,快速搅拌均匀,过滤后喷雾干燥造粒、焙烧、洗涤、过滤,获得的颗粒物记作A。
(2)将N-甲基二乙醇胺模板剂加入硫酸铝溶液中,搅拌均匀,将该浆液记作B。
(3)将A用水打浆,水玻璃与B并流加入浆液A中,混合均匀后升温晶化。
(4)晶化完毕,过滤、洗涤、干燥后得到标题物。
2.根据权利要求1所述的制备方法,其特征在于:步骤(1)中ZSM-5分子筛硅铝比为60-120,硫酸铝以氧化铝计,硅溶胶以氧化硅计,其与ZSM-5分子筛三者的质量比为(0.12-0.30):(0.06-0.10):1。
3.根据权利要求1所述的制备方法,其特征在于:步骤(1)中焙烧温度为400-450℃,洗涤后要求SO4 2-≤5.0wt%。
4.根据权利要求1所述的制备方法,其特征在于:步骤(2)中N-甲基二乙醇胺加入比例与以氧化铝计的硫酸铝的质量比为(0.001-0.01):1。
5.根据权利要求1所述的制备方法,其特征在于:步骤(3)中,各物料加入比例以摩尔计为A(以ZSM-5中的Al2O3计):水玻璃(以SiO2计):硫酸铝(以Al2O3计):模板剂:H2O=(0.8-4.0):(250-500):1:(0.05-0.25):(800-1000)。
6.根据权利要求1所述的制备方法,其特征在于:步骤(4)中,洗涤液中应含有硫酸铵,洗涤后催化剂中的氧化纳含量应小于0.2wt%。
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