CN111939970A - 一种提高催化裂化汽油辛烷值助剂的制备方法 - Google Patents
一种提高催化裂化汽油辛烷值助剂的制备方法 Download PDFInfo
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- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 45
- 239000003502 gasoline Substances 0.000 title claims abstract description 45
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 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 39
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 37
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001914 filtration Methods 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 7
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 7
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims description 16
- 239000004005 microsphere Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910002249 LaCl3 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003254 gasoline additive Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003375 selectivity assay Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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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
- B01J29/40—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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- 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
- B01J29/42—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 iron group metals, noble metals or copper
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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Abstract
本发明属于催化裂化助剂制备技术领域，公开一种提高催化裂化汽油辛烷值助剂的制备方法，包括：(1)将高岭土浸渍碱性溶液，焙烧得焙烧高岭土；(2)将焙烧高岭土、白炭黑、水玻璃、氢氧化钠、晶种和去离子水投入晶化反应釜中，水热晶化30‑90h，过滤干燥到ZSM‑5分子筛；(3)将ZSM‑5分子筛进行交换过滤得HZSM‑5分子筛；(4)将HZSM‑5分子筛经过改性，过滤、干燥、焙烧得改性HZSM‑5分子筛；(5)将改性HZSM‑5分子筛、粘结剂、助剂、去离子水搅拌混合形成浆液，喷雾干燥，焙烧制得增产催化裂化汽油辛烷值助剂。本发明制备的提高催化裂化汽油辛烷值助剂用于催化裂化过程，能够有效地提高汽油辛烷值。
Description
技术领域
本发明属于催化裂化助剂制备技术领域，涉及一种提高催化裂化汽油辛烷值助剂的制备方法。
背景技术
催化裂化汽油是我国车用汽油的主要组成部分，在汽油中占75％左右。我国车用汽油的商品牌号是以辛烷值来划分的，辛烷值是表示汽化器式发动机燃料的抗爆性能好坏的一项重要指标，其辛烷值的高低直接影响着成品汽油的辛烷值水平。汽车发动机的压缩比和汽油耗量、燃油经济性有直接关系，压缩比增加一个单位，可改善燃油经济性4％～12％；汽油辛烷值增加一个单位，可以降低油耗0.7％～3.1％。为了高压缩比汽车发动机的正常工作以及环保法规的日益严格，必须使用高辛烷值的汽油才能满足要求。
催化裂化汽油辛烷值的高低对汽油辛烷值总体水平起着举足轻重的作用，提高催化裂化汽油的辛烷值是提高成品汽油辛烷值的关键。目前采用高辛烷值催化剂或助剂是提高催化裂化汽油辛烷值最为经济有效的措施。目前，普通方法制备的助剂无裂化活性，加入比例超过5％后，影响产品分布，重油升高，高附加值、轻收组分减少，另外使用过量的磷铝胶，导致分子筛孔道被堵，活性、选择性降低，而且磷元素进入FCC粉尘，回收粉尘对零部件产生不利影响。
发明内容
本发明要解决的技术问题是克服上述缺陷，提供一种活性高、水热稳定性好成本低廉的提高催化裂化汽油辛烷值助剂的制备方法。
为了解决上述技术问题，本发明的技术方案为：
一种提高催化裂化汽油辛烷值助剂的制备方法，包括如下步骤：
(1)将高岭土浸渍碱性溶液，放置0.5-5h，在700～1000℃下焙烧0.5～5小时，粉碎，得焙烧高岭土；
(2)将步骤(1)得到的焙烧高岭土、白炭黑、水玻璃、氢氧化钠、晶种和去离子水投入晶化反应釜中，用酸将浆液终点pH调至11～12，在150-190℃下水热晶化30-90h，过滤除去母液后，滤料水洗，过滤，干燥得到ZSM-5分子筛；
(3)将步骤(2)得到的ZSM-5分子筛进行2-5次酸交换，室温下交换10～30min，过滤、水洗、过滤后，得HZSM-5分子筛；
(4)将步骤(3)得到的HZSM-5分子筛经过稀土、锌、镁、镍中两种或两种以上元素的混合改性，室温下改性10～30min，过滤除去母液后，水洗滤料，过滤，干燥，550～650℃下焙烧0.5～3小时，得改性HZSM-5分子筛；
(5)将步骤(4)得到的改性HZSM-5分子筛、粘结剂、助剂、去离子水混合形成浆液，浆液在50～80℃温度下搅拌0.5～2h，使之分散均匀，浆液进行喷雾干燥，得喷雾微球，将喷雾微球在400～600℃温度下焙烧0.5～2h，制得提高催化裂化汽油辛烷值助剂。
优选的，步骤(1)所述碱性溶液为氢氧化钠、硅酸钠、偏铝酸钠、氢氧化钾、碳酸钠等中的一种或几种。
优选的，步骤(1)所述高岭土粉碎颗粒粒径≦5μm。
优选的，步骤(2)所述白炭黑的加入量为焙烧高岭土质量的30～50％。
优选的，步骤(2)所述晶种为ZSM-5、Y型、X型分子筛中的任意一种。
优选的，步骤(2)所述晶种的加入量为焙烧高岭土质量的1～10％。
优选的，步骤(5)所述粘结剂为硅溶胶、铝溶胶、硅铝溶胶中的任意一种，所述粘结剂的加入量为步骤(5)固体总重15～30％。
优选的，步骤(5)所述助剂为高岭土、改性高岭土、氧化硼、氧化锆中的一种或几种。
优选的，步骤(5)所述助剂的加入量为步骤(5)固体总重15-30％。
与现有技术相比本发明的有益效果是：
(1)本发明助剂采用原位法合成，具有较高的硅铝比，硅铝比的分子筛可以有效控制催化裂化过程中氢转移反应，从而尽量减小汽油转化为液化气所带来的收率损失；同时将原位技术的特性及粘结技术的协同使用，使得助剂具有优良的抗磨损性能，减少提助剂在使用过程中的消耗。
(2)本发明采用的活性组分对分子筛的改性及与助剂产生协同效应，优化了酸中心数量和酸强度，有效调节和优化助剂的孔道分布，丰富了助剂内部的中大孔结构，特别是大孔比列，阻止了孔道的堆积，提高了本发明的催化裂化提高汽油辛烷值助剂的活性和抗杂质污染能力。
(3)本发明提供的催化裂化助剂具有活性高、水热稳定性好的特点，用于催化裂化过程，能够有效地提高汽油辛烷值。
附图说明
图1为实施例3合成ZSM-5的XRD图
具体实施方式
以下对本发明专利的原理和特征进行描述，所举实例只用于解释本发明专利，并非用于限定本发明专利的范围。
实施例1
一种提高催化裂化汽油辛烷值助剂的制备方法，包括如下步骤：
(1)将15％的偏铝酸钠溶液70mL浸渍到300g高岭土0.5h，浸渍高岭土在700℃下焙烧5小时，粉碎高岭土颗粒粒径≦5μm，得焙烧高岭土；
(2)将100g焙烧高岭土、100g白炭黑、746mL水玻璃、97mL氢氧化钠、6g ZSM-5分子筛和2300mL去离子水投入晶化反应釜中，用硫酸将浆液终点pH调至11～12，在150℃下水热晶化90h，过滤除去母液后，滤料水洗，过滤，干燥得到ZSM-5分子筛；
(3)将步骤(2)得到的ZSM-5分子筛100g、300mL去离子水，加入盐酸控制pH＝1.5，室温下交换10min，过滤、水洗、过滤后，以上步骤重复2次，得HZSM-5分子筛；
(4)将步骤(3)得到的80gHZSM-5分子筛、LaCl3溶液30mL、氯化锌4g、320mL去离子水加入到反应釜中进行改性，室温下交换10min，过滤除去母液后，水洗滤料，过滤，干燥，650℃下焙烧0.5小时，得到改性ZSM-5分子筛；
(5)将步骤(4)得到的改性ZSM-5分子筛60g、铝溶胶20g、氧化硼20g、去离子水500mL，混合形成浆液，浆液在50℃温度下搅拌2h，使之分散均匀，浆液进行喷雾干燥，得喷雾微球，将喷雾微球在400℃温度下焙烧2h，制得提高催化裂化汽油辛烷值助剂。
实施例2
一种提高催化裂化汽油辛烷值助剂的制备方法，包括如下步骤：
(1)将27％的硅酸钠溶液56mL浸渍到400g高岭土2h，浸渍高岭土在800℃下焙烧3小时，粉碎高岭土颗粒粒径≦5μm，得焙烧高岭土；
(2)将100g焙烧高岭土、66g白炭黑、800mL水玻璃、80mL氢氧化钠、17gY型分子筛和1700mL去离子水投入晶化反应釜中，用酸将浆液终点pH调至11～12，在160℃下水热晶化80h，过滤除去母液后，滤料水洗，过滤，干燥得到ZSM-5分子筛；
(3)将步骤(2)得到的ZSM-5分子筛100g、300mL去离子水，加入硫酸控制pH＝2.0，室温下交换20min，过滤、水洗、过滤后，以上步骤重复2次，得HZSM-5分子筛；
(4)将步骤(3)得到的80gHZSM-5分子筛、LaCl3溶液20mL、氯化镁5g、240mL去离子水加入到反应釜中进行改性，室温下交换20min，过滤除去母液后，水洗滤料，过滤，干燥，550℃下焙烧3小时，得到改性ZSM-5分子筛；
(5)将步骤(4)得到的改性ZSM-5分子筛70g、硅铝溶胶15g、氧化硼15g、去离子水600mL，混合形成浆液，浆液在60℃温度下搅拌1.5h，使之分散均匀，浆液进行喷雾干燥，得喷雾微球，将喷雾微球在600℃温度下焙烧0.5h，制得提高催化裂化汽油辛烷值助剂。
实施例3
一种提高催化裂化汽油辛烷值助剂的制备方法，包括如下步骤：
(1)将15％的氢氧化钠溶液28mL浸渍到500g高岭土上，放置3h，浸渍高岭土在900℃下焙烧2h，粉碎高岭土颗粒粒径≦5μm，得焙烧高岭土；
(2)将100g焙烧高岭土、50g白炭黑、750mL水玻璃、74mL氢氧化钠、1.5g ZSM-5和1770mL去离子水投入晶化反应釜中，用酸将浆液终点pH调至11～12，在170℃下水热晶化50h，过滤除去母液后，滤料水洗，过滤，干燥得到ZSM-5分子筛；
(3)将步骤(2)得到的ZSM-5分子筛100g、300mL去离子水，加入盐酸控制pH＝2.5，室温下交换30min，过滤、水洗、过滤后，以上步骤重复1次，得HZSM-5分子筛；
(4)将步骤(3)得到的80gHZSM-5分子筛、LaCl3溶液40mL、氯化锌7g、400mL去离子水加入到反应釜中进行改性，室温下交换30min，过滤除去母液后，水洗滤料，过滤，干燥，600℃下焙烧2h，得到改性ZSM-5分子筛；
(5)将步骤(4)得到的改性ZSM-5分子筛70g、硅溶胶47g、高岭土39g、去离子水600mL，混合形成浆液，浆液在70℃温度下搅拌1h，使之分散均匀，浆液进行喷雾干燥，得喷雾微球，将喷雾微球在600℃温度下焙烧0.5h，制得提高催化裂化汽油辛烷值助剂。
实施例4
一种提高催化裂化汽油辛烷值助剂的制备方法，包括如下步骤：
(1)将15％的碳酸钠溶液35mL浸渍到200g高岭土5h，浸渍高岭土在1000℃下焙烧0.5小时，粉碎高岭土颗粒粒径≦5μm，得焙烧高岭土；
(2)将100g焙烧高岭土、43g白炭黑、713mL水玻璃、71mL氢氧化钠、10gX型分子筛和1700mL去离子水投入晶化反应釜中，用酸将浆液终点pH调至11～12，在190℃下水热晶化30h，过滤除去母液后，滤料水洗，过滤，干燥得到ZSM-5分子筛；
(3)将步骤(2)得到的ZSM-5分子筛100g、300mL去离子水，加入硝酸控制pH＝1.5，室温下交换30min，过滤、水洗、过滤后，以上步骤重复1次，得HZSM-5分子筛；
(4)将步骤(3)得到的80gHZSM-5分子筛、LaCl3溶液35mL、氯化镍2g、400mL去离子水加入到反应釜中进行改性，室温下交换30min，过滤除去母液后，水洗滤料，过滤，干燥，650℃下焙烧0.5小时，得到改性ZSM-5分子筛；
(5)将步骤(4)得到的改性ZSM-5分子筛78g、铝溶胶31g、氧化锆47g、去离子水600mL，混合形成浆液，浆液在80℃温度下搅拌0.5h，使之分散均匀，浆液进行喷雾干燥，得喷雾微球，将喷雾微球在600℃温度下焙烧0.5h，制得提高催化裂化汽油辛烷值助剂。
其中，X-射线衍射测定方法：采用日本理学Rigaku-D-MaxrA 12kW型X射线衍射仪(XRD)进行样品的物相分析，测试条件：Cu靶，波长λ＝1.54056nm，管电压40kV，管电流40mA，发散狭缝和散射狭缝扫描速度为8°/min。
反应活性及选择性检测
采用ACE评价产品的反应活性及选择性。主剂和实施例1-4制备的助剂均经过800℃、17小时、100％水蒸汽老化，然后以5％的助剂用量与主剂混合进行评价，分为对照组和实验组，其中对照组为主剂，实验组分别是主剂添加5％的实施例1-4制备的助剂，分别为实验组1-4。具体评价结果见表1。
| 项目 | 对照组 | 实验组1 | 实验组2 | 实验组3 | 实验组4 |
| 温度/℃ | 500 | 500 | 500 | 500 | 500 |
| 剂油比 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 |
| 干气 | 1.78 | 1.81 | 1.88 | 1.84 | 1.80 |
| 液化气 | 15.45 | 17.46 | 17.61 | 17.73 | 17.39 |
| 汽油 | 48.96 | 46.15 | 45.91 | 45.81 | 45.77 |
| 柴油 | 17.34 | 18.81 | 18.35 | 18.53 | 18.86 |
| 重油 | 9.55 | 9.01 | 9.69 | 9.25 | 9.20 |
| 焦碳 | 6.92 | 6.76 | 6.56 | 6.84 | 6.98 |
| 转化率/m％ | 71.11 | 72.18 | 71.96 | 72.22 | 71.94 |
| RON辛烷值 | 92.2 | 93.7 | 93.4 | 93.3 | 93.5 |
从表上数据可以看出，添加本发明制备的增产催化裂化汽油辛烷值助剂均表现出增产辛烷值能力强、焦炭选择性好的特点，尤其是实施例3制备的增产催化裂化汽油辛烷值助剂的性能优。
以上为本发明较佳实施例，只适用于帮助理解本发明实施例的原理；同时，对于本领域的一般技术人员，依据本实施例，在具体实施方式以及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。对于本领域技术人员而言，显然本发明专利不限于上述示范性实施例的细节，而且在不背离本发明专利的精神或基本特征的情况下，能够以其它的具体形式实现本发明专利。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明专利的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明专利内，不应将权利要求中的任何附图标记视为限制所涉及的权利要求。
以上所述仅为本发明专利的较佳实施例，并不用以限制本发明专利，凡在本发明专利的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明专利的保护范围之内。
Claims (8)
1.一种提高催化裂化汽油辛烷值助剂的制备方法，其特征在于：包括如下步骤：
(1)将高岭土浸渍碱性溶液，放置0.5-5h，在700～1000℃下焙烧0.5～5小时，粉碎，得焙烧高岭土；
(2)将步骤(1)得到的焙烧高岭土、白炭黑、水玻璃、氢氧化钠、晶种和去离子水投入晶化反应釜中，用酸将浆液终点pH调至11～12，在150-190℃下水热晶化30-90h，过滤除去母液后，滤料水洗，过滤，干燥得到ZSM-5分子筛；
(3)将步骤(2)得到的ZSM-5分子筛进行2-5次酸交换，室温下交换10～30min，过滤、水洗、过滤后，得HZSM-5分子筛；
(4)将步骤(3)得到的HZSM-5分子筛经过稀土、锌、镁、镍中两种或两种以上元素的混合改性，室温下改性10～30min，过滤除去母液后，水洗滤料，过滤，干燥，550～650℃下焙烧0.5～3小时，得改性HZSM-5分子筛；
(5)将步骤(4)得到的改性HZSM-5分子筛、粘结剂、助剂、去离子水混合形成浆液，浆液在50～80℃温度下搅拌0.5～2h，使之分散均匀，浆液进行喷雾干燥，得喷雾微球，将喷雾微球在400～600℃温度下焙烧0.5～2h，制得增产催化裂化汽油辛烷值助剂。
2.根据权利要求1所述的提高催化裂化汽油辛烷值助剂的制备方法，其特征在于：步骤(1)所述碱性溶液为氢氧化钠、硅酸钠、偏铝酸钠、氢氧化钾、碳酸钠等中的一种或几种。
3.根据权利要求1所述的提高催化裂化汽油辛烷值助剂的制备方法，其特征在于：步骤(1)所述高岭土粉碎颗粒粒径≦5μm。
4.根据权利要求3所述的提高催化裂化汽油辛烷值助剂的制备方法，其特征在于：步骤(2)所述白炭黑的加入量为焙烧高岭土质量的30～50％。
5.根据权利要求1所述的提高催化裂化汽油辛烷值助剂的制备方法，其特征在于：步骤(2)所述晶种为ZSM-5、Y型、X型分子筛中的任意一种，所述晶种的加入量为步骤(2)固体总重1～10％。
6.根据权利要求1所述的提高催化裂化汽油辛烷值助剂的制备方法，其特征在于：步骤(5)所述粘结剂为硅溶胶、铝溶胶、硅铝溶胶中的任意一种，所述粘结剂的加入量为步骤(5)固体总重15-30％。
7.根据权利要求1所述的提高催化裂化汽油辛烷值助剂的制备方法，其特征在于：步骤(5)所述助剂为高岭土、改性高岭土、氧化硼、氧化锆中的一种或几种。
8.根据权利要求1所述的提高催化裂化汽油辛烷值助剂的制备方法，其特征在于：步骤(5)所述助剂的加入量为步骤(5)固体总重15～30％。
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