CN114471678B - 异构脱蜡催化剂及其制备方法与生产润滑油基础油的方法 - Google Patents
异构脱蜡催化剂及其制备方法与生产润滑油基础油的方法 Download PDFInfo
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- CN114471678B CN114471678B CN202011258641.9A CN202011258641A CN114471678B CN 114471678 B CN114471678 B CN 114471678B CN 202011258641 A CN202011258641 A CN 202011258641A CN 114471678 B CN114471678 B CN 114471678B
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- oil
- catalyst
- acid
- base oil
- salt
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- 239000002199 base oil Substances 0.000 title claims abstract description 138
- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 76
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003921 oil Substances 0.000 claims abstract description 95
- 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 60
- 238000012986 modification Methods 0.000 claims abstract description 47
- 230000004048 modification Effects 0.000 claims abstract description 47
- 239000002253 acid Substances 0.000 claims abstract description 45
- 239000002808 molecular sieve Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 230000001050 lubricating effect Effects 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007670 refining Methods 0.000 claims abstract description 20
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 59
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000314 lubricant Substances 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 159000000009 barium salts Chemical class 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 150000002258 gallium Chemical class 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 159000000008 strontium salts Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 31
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 14
- 239000012266 salt solution Substances 0.000 abstract description 5
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 3
- 230000000052 comparative effect Effects 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- -1 alkali metal salt Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000000295 complement effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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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
- 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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- 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
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- 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
- B01J29/44—Noble metals
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- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
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- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/74—Noble metals
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- B01J29/7446—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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- B01J29/74—Noble metals
- B01J29/7461—MRE-type, e.g. ZSM-48
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/74—Noble metals
- B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
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Abstract
本发明提供一种异构脱蜡催化剂及其制备方法与生产润滑油基础油的方法。该异构脱蜡催化剂的制备方法包括:将含十元环结构的未成型分子筛进行碱金属盐的溶液和/或酸溶液改性得到第一次改性后的分子筛,经成型处理后用碱金属盐的溶液和/或酸溶液进行第二次改性,然后将贵金属活性组分负载其上得到异构脱蜡催化剂。生产润滑油基础油的方法包括:含蜡油与氢气的混合物依次与至少两种异构脱蜡催化剂进行异构化和裂化反应,反应产物与氢气混合后与补充精制催化剂进行芳烃饱和反应,反应产物经分馏得到润滑油基础油。使用上述异构脱蜡催化剂及生产润滑油基础油的方法制备得到的润滑油基础油实现了浊点的大幅度降低。
Description
技术领域
本发明属于润滑油基础油领域,特别涉及一种异构脱蜡催化剂及其制备方法与生产润滑油基础油的方法。
背景技术
润滑油生产的常规方法是老三套生产工艺(溶剂精制-溶剂脱蜡-白土精制)该种方法生产的基础油饱和烃含量一般都小于90%,硫、氮含量较高,颜色较深,同时该种方法对生产基础油的原料质量依赖性较大,中间基原油较难生产出高粘度指数基础油,通常所生产的基础油为I类基础油,无法生产粘度指数高,倾点低的II类及III类基础油,更不能生产低浊点的润滑油基础油。
随着工业的发展,尤其是汽车工业的发展,对基础油的质量提出更高的要求,一方面希望从中间基原油生产高粘度指数的基础油,另一方面,通过对高凝点蜡油进行异构,希望得到很高或超高粘度指数的基础油,这就推动了催化脱蜡技术和异构脱蜡技术的发展。
催化脱蜡技术最早由Mobil公司在20世纪70年代提出,主要是利用催化剂的择型功能,选择性地将直链正构烷烃和带有长测链的烃类,裂化为小分子烃类,蜡分子在催化剂上发生选择性裂解而除去,达到降低基础油倾点的目的,对浊点效果不明显,但是该种方法蜡分子的选择性裂解会导致基础油收率和黏度指数的下降,其黏度指数一般比溶剂脱蜡的低。
异构脱蜡技术在20世纪90年代由Chevron公司提出,在临氢条件下,利用催化剂对正构烷烃的异构功能,将正构烷烃异构化,所以其基础油收率和黏度指数都比催化脱蜡高,异构脱蜡技术被认为是最有前途的II类及III类基础油生产技术。润滑油基础油异构脱蜡技术核心就是需要有高选择性的异构脱蜡催化剂,通常是在双功能催化剂上连续进行异构化和加氢裂化反应,反应过程以异构化反应为主。
异构脱蜡技术生产的基础油,虽然具有硫、氮含量低、颜色透明、黏度指数高、倾点低的优点,但是由于不能一些结构复杂的蜡分子不能被完全转化,使得基础油在室温或较低温度放置一段时间后,常常伴有絮状物从基础油中析出,特别是黏度高的重质基础油,虽然有较低的倾点,但是浊点很高,浊点一般在5℃以上,甚至达到10-20℃絮状物不但影响基础油的外观,同时对其它性质也有一定的影响。
为了降低基础油的浊点,研究者从多方面探索采用不同方法降低基础油的浊点。
US6468417和US6468418介绍用酸性白土或氧化铝作吸附剂在特定的容器内处理基础油,由于蜡分子的竞争吸附作用,使基础油的浊点降低,但是降低程度有限。吸附剂床层吸附一段时间后(吸附饱和),就要采用加热方法回收吸附的蜡,然后才能再进行吸附,操作起来比较复杂,尤其当处理重质基础油时,由于其黏度较大,基础油通过吸附剂床层时非常困难,即使采用溶剂稀释在工业上实施也较为困难。
US4950382介绍先采用溶剂脱蜡或催化脱蜡使基础油的倾点降低,然后再采用非极性,不具有酸性,孔口尺寸在的分子筛进行吸附脱蜡,然后再加入添加剂提高粘指和降低倾点,该种方法对于基础油降低效果也有限。
US7674363介绍先采用异构脱蜡方法再进行溶剂脱蜡处理费托合成油,虽然该种方法在基础油降低倾点方面比较有效,但是基础油蜡含量在-20℃处理后仍含有30%以上,因此不能有效降低基础油的浊点。
US8449760介绍一种通过油品调和方法来提高基础油性质的方法,是将倾点高低沸点的F-T合成油混入高沸点的馏分油中,制备出浊点不高于0℃的基础油,这样通过物理调和手段不能真正的从实际意义将正构蜡分子转变成异构分子,因此也不可能有效降低浊点。
CN101223262A介绍将100℃下运动黏度大于10cst的基础油分理出导致高浊点的分子,将高浊点基础油通过冷却表面使高浊点蜡分子分离出来,从而降低基础油的浊点。在冷却表面吸附的蜡分子分通过熔融方法分离下来,再重新使用冷却表面即可,该种方法可以制备出浊点不大于15℃的基础油,对于工业装置来实施起来还要增加配套装置,实施过程比较复杂,更重要的是不能有效降低基础油的浊点。
发明内容
本发明的目的在于提供一种适用于高凝点含蜡油生产低浊点润滑油基础油的异构脱蜡催化剂以及工艺方法,使用该催化剂以及该工艺方法进行高凝点含蜡油生产润滑油基础油有效解决了现有润滑油基础油生产过程中浊点偏高的问题。
为了实现上述目的,本发明提供了一种异构脱蜡催化剂的制备方法,该方法包括:
1)将含十元环结构的未成型分子筛使用改性剂进行第一次改性,经过干燥和焙烧处理得到第一次改性后的分子筛;所述第一次改性使用的改性剂包括碱金属盐的溶液和/或酸溶液;
2)将第一次改性后的分子筛成型后使用改性剂进行第二次改性,经过干燥和焙烧处理得到第二次改性后的分子筛;所述第二次改性使用的改性剂包括碱金属盐的溶液和/或酸溶液;
3)将贵金属活性组分负载到第二次改性后的分子筛上,经干燥、焙烧得到所述异构脱蜡催化剂。
在上述制备方法中,优选地,所述含十元环结构的未成型分子筛具有直通孔道结构。
在上述制备方法中,优选地,含十元环结构的未成型分子筛包括ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-22、MCM-22、NU-87、ZSM-23、ZSM-35、ZSM-48和他们复合分子筛中的一种或两种以上的组合。
在上述制备方法中,优选地,在步骤1)中,所述碱金属盐的溶液中碱金属盐的浓度为0.1-0.5mol/L,酸溶液中酸的浓度为0.1-0.5mol/L。更优选地,含十元环结构的未成型分子筛与第一次改性使用的改性剂的体积之比为100g:50-70mL。
在上述制备方法中,优选地,在步骤2)中,所述碱金属盐的溶液中碱金属盐的浓度为0.1-0.5mol/L,酸溶液中酸的浓度为0.1-0.5mol/L。更优选地,第一次改性后的分子筛与第二次改性使用的改性剂的体积之比为1g:2mL。
在上述制备方法中,优选地,所述贵金属活性组分包括Pt、Pd、Ru、Rh、Re和Ir中的一种或两种以上的组合;更优选地,所述贵金属活性组分包括Pt和Pd;进一步优选地,在异构脱蜡催化剂,Pt和Pd含量分别为0.1-1wt%和0.1-1wt%。
在上述制备方法中,优选地,在异构脱蜡催化剂中,所述单种贵金属活性组分占催化剂质量含量为0.1-0.5%。
在上述制备方法中,优选地,步骤1)所述碱金属盐包括IA、IIA、IIIA、IB和/或IIB族金属盐;更优选地,所述碱金属盐包括钾盐、镁盐、钙盐、锶盐、钡盐、铜盐、锌盐、镓盐、锡盐中的一种或两种以上的组合。
在上述制备方法中,优选地,步骤1)所述酸包括硝酸、磷酸、醋酸、酒石酸、柠檬酸中的一种或两种以上的组合。
在上述制备方法中,优选地,步骤2)所述碱金属盐包括IA、IIA、IIIA、IB和/或IIB族金属盐溶液;更优选地,所述碱金属盐包括钾盐、镁盐、钙盐、锶盐、钡盐、铜盐、锌盐、镓盐、锡盐中的一种或两种以上的组合。
在上述制备方法中,优选地,步骤2)所述酸包括硝酸、磷酸、醋酸、酒石酸、柠檬酸中的一种或两种以上的组合。
在上述制备方法中,优选地,步骤1)所述焙烧的温度为300-600℃,焙烧时间为4-10小时。
在上述制备方法中,优选地,步骤2)所述焙烧的温度为300-600℃,焙烧时间为5-20小时。
在上述制备方法中,优选地,所述成型通过下述方式实现:将第一次改性后的分子筛与氧化铝混捏,经挤压成型、干燥实现将第一次改性后的分子筛成型。在优选实施方式中,将第一次改性后的分子筛与氧化铝粉混捏,经挤压成型、干燥实现将第一次改性后的分子筛成型,其中,第一次改性后的分子筛与氧化铝粉的质量比为1:5-5:1。
在上述制备方法中,优选地,步骤3)所述将贵金属活性组分负载到第二次改性后的分子筛上通过下述方式实现:采用等体积浸渍方法将贵金属活性组分前驱体溶液浸渍到第二次改性后的分子筛上,经干燥、焙烧得到所述异构脱蜡催化剂,其中所述焙烧的温度为300-600℃,焙烧时间为5-20小时。
在上述制备方法中,优选地,所述第一次改性后的分子筛,150℃时测试B酸含量在0.2-0.6mmol/g,B酸含量:L酸含量=6:1-1:1;350℃时测试B酸含量在0.05-0.4mmol/g,B酸含量:L酸含量=6:1-1:1;其中150℃时的B酸与L酸的含量和>350℃时的B酸与L酸的含量和;其中酸类型及酸含量的测定优选采用吡啶-红外(Py-IR)方法进行。
本发明还提供一种上述异构脱蜡催化剂的制备方法制备得到的异构脱蜡催化剂。
本发明还提供一种生产润滑油基础油的方法,其中,该方法包括:
A、含蜡油与氢气预混形成氢油混合物,氢油混合物依次与至少两种上述异构脱蜡催化剂进行反应实现含蜡油异构化反应和裂化反应,生成油M;所述至少两种异构脱蜡催化剂选自上述的异构脱蜡催化剂;
B、将油M与氢气混合后与补充精制催化剂进行芳烃饱和反应,生成的产物经分馏得到润滑油基础油;
含蜡油凝点不高于70℃,蜡含量不高于80wt%,芳烃含量不高于50wt%,硫含量不高于100μg/g,氮含量不高于50μg/g,含蜡油的馏程范围为300-600℃。
在上述生产润滑油基础油的方法中,所述含蜡油优选使用高凝点含蜡油。高凝点的含蜡油可用于制备粘度高、粘度指数高的基础油。
在上述生产润滑油基础油的方法中,优选地,所述补充精制催化剂的活性组分为贵金属催化剂;更优选地,所述补充精制催化剂的活性组分至少含有Pt、Pd、Ru、Rh、Re和Ir中的一种元素,活性组分占补充精制催化剂质量的0.1-1.0wt%,补充精制催化剂的载体由氧化铝、无定形硅铝、二氧化钛、二氧化锆和二氧化硅中一种或几种制备而来。
在上述生产润滑油基础油的方法中,优选地,所述含蜡油选自减压蜡油、减压脱蜡油、加氢裂化尾油、脱沥青油、焦化蜡油中的一种或两种以上的组合。
在上述生产润滑油基础油的方法中,优选地,在步骤A中所述异构化反应和裂化反应的温度为300-400℃、压力为8-16MPa。
在上述生产润滑油基础油的方法中,优选地,在步骤B中所述芳烃饱和反应的温度为150-300℃、压力为8-16MPa。
在上述生产润滑油基础油的方法中,优选地,所述含蜡油凝点不高于60℃,蜡含量不高于70wt%,芳烃含量不高于50wt%,硫含量不高于100μg/g,氮含量不高于50μg/g,含蜡油的馏程终馏点不高于600℃。更优选地,所述含蜡油凝点不高于50℃,蜡含量不高于60wt%,芳烃含量不高于40wt%,硫含量不高于50μg/g,氮含量不高于20μg/g,含蜡油的馏程终馏点不高于580℃。
在优选实施方式中,上述生产润滑油基础油的方法包括:
A、含蜡油与氢气预混形成氢油混合物,氢油混合物进入异构脱蜡反应器,与异构脱蜡反应器中的异构脱蜡催化剂进行异构化反应和裂化反应,生成油M;其中异构脱蜡反应器包括至少两个床层,异构脱蜡反应器中装填至少两种异构脱蜡催化剂;所述至少两种异构脱蜡催化剂选自本发明提供的上述异构脱蜡催化剂;
B、将油M与氢气混合后与补充精制催化剂进行芳烃饱和反应,生成的产物经分馏得到润滑油基础油;
含蜡油凝点不高于70℃,蜡含量不高于80wt%,芳烃含量不高于50wt%,硫含量不高于100μg/g,氮含量不高于50μg/g,含蜡油的馏程范围为300-600℃。
本发明还提供一种上述生产润滑油基础油的方法制备得到的润滑油基础油,其中,该润滑油基础油的浊点不高于-5℃;
在上述润滑油基础油中,优选地,所述润滑油基础油的浊点不高于-8℃;更优选地,所述润滑油基础油的浊点不高于-15℃。
本发明还提供一种生产润滑油基础油的装置,该装置包括:异构脱蜡反应器、补充精制反应器和分馏系统;其中,
异构脱蜡反应器与补充精制反应器连接,补充精致反应器与分馏系统连接;
所述异构脱蜡反应器包括至少两个床层,异构脱蜡反应器中装填至少两种异构脱蜡催化剂;所述异构脱蜡反应器用以实现含蜡油与氢气混合后与异构脱蜡反应器中的异构脱蜡催化剂进行异构化反应和裂化反应;所述至少两种异构脱蜡催化剂选自本发明提供的上述异构脱蜡催化剂;
所述补充精制反应器用以实现异构脱蜡反应器中反应生成的产物与氢气混合后进行芳烃饱和反应;
所述分馏系统用以实现对补充精制反应器中得到的产物的分馏得到润滑油基础油。
本发明提供的技术方案实现了对润滑油基础油中大分子转化能力的显著提高,可以有效的将蜡分子进行异构化,降低基础油的浊点。与现有技术相比,本发明技术方案具备以下优势:
(1)本发明提供的异构脱蜡催化剂性能优异,特别适用于润滑油基础油的生产;当利用本发明提供的异构脱蜡催化剂,通过临氢加氢异构方法处理含蜡油生产润滑油基础油时,基础油收率高;并且制得的基础油产品性能优异。
(2)本发明提供的生产润滑油基础油的方法实现了低浊点润滑油基础油的制备,该方法制备得到的润滑油基础油的浊点大幅度降低,制得的润滑油基础油浊点不高于-5℃即使是以高凝点含蜡油为原料其浊点依旧不高于-5℃(在优选实施方式中,通过采用不同种类催化剂,并调整催化剂的级配,可实现浊点不高于-8℃(如实施例18所示)甚至-15℃(如实施例16所示));同时制得的润滑油基础油还兼具倾点低、芳烃含量低等优点。
(3)本发明提供的生产润滑油基础油的方法能够适用于以高凝点含蜡油为原料生产润滑油基础油,对于以高凝点含蜡油为原料生产润滑油基础油表现出优异的处理能力;具有芳烃饱和性能强、加氢异构性能好、基础油收率高、降低基础油倾点、提高浊点性能的优势,尤其是实现了生产粘度和粘度指数较高且低浊点的润滑油基础油。
(4)本发明提供的润滑油基础油的生产方法能够适用于处理减压蜡油、减压脱蜡油、加氢裂化尾油、脱沥青油、焦化蜡油等,尤其适用于以重质高凝点含蜡油为原料生产低浊点高档润滑油基础油,应用前景广阔。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解,现对本发明的技术方案进行以下详细说明,但不能理解为对本发明的可实施范围的限定。
实施例1
将市售工业应用分子筛原粉ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-22、MCM-22、NU-87、ZSM-23、ZSM-35、ZSM-48分别用浓度为0.1-0.5mol/L的碱金属盐的溶液和/或浓度为0.1-0.5mol/L的酸性溶液进行改性(具体改性方法为用碱金属盐的溶液和/或酸性溶液浸渍分子筛原粉),其中,分子筛原粉质量与改性溶液的体积之比为100g:50-70mL,改性后分子筛然后经干燥和550℃焙烧4-10小时处理得到第一次改性后的分子筛;其中,上述各分子筛分别取100g进行说明,上述分子筛的Si/Al2O3摩尔比为0.5-120、平均晶粒大小为50-100nm,改性后的产品以及改性试剂等如表1所示。
表1
对各第一次改性后的分子筛进行吡啶红外(Py-IR)吸附-脱附表征,具体为:将各第一次改性后的分子筛分别放在吡啶样品池中经过抽真空前处理,在0℃冰浴的吡啶样品池中吸附饱和后,经150℃和350℃吡啶脱附表征,计算出样品的B酸和L酸量,表征结果见表2。
表2
实施例2
本实施例提供一种异构脱蜡催化剂A1,其制备方法具体如下:
1)将70g实施例1中制备得到的第一次改性后的分子筛A1与40g氧化铝粉混捏,经过挤条成型得到湿条;将湿条于200℃干燥5小时后使用0.1mol/L KCl溶液200ml进行浸渍实现第二次改性,然后经100℃干燥、550℃焙烧5小时后制备得到第二次改性后的分子筛即催化剂载体;
2)采用等体积浸渍方法将含PtCl2和PdCl2的溶液浸渍到催化剂载体上(即第二次改性后的分子筛),然后经120℃干燥、550℃焙烧4小时制备成催化剂A1;其中,在催化剂A1中Pt和Pd含量分别为0.3wt%和0.2wt%(以催化剂质量计)。
实施例3
本实施例提供一种异构脱蜡催化剂A2,其制备方法与实施例2的区别仅在于:使用100g实施例1中制备得到的第一次改性后的分子筛A1与20g氧化铝粉混捏,两次焙烧温度皆为450℃,焙烧时间皆为10小时,在催化剂A2中Pt和Pd含量分别为1.0wt%和0.1wt%(以催化剂质量计),其他均与实施例2相同。
实施例4
本实施例提供一种异构脱蜡催化剂A3,其制备方法与实施例2的区别仅在于:使用50g实施例1中制备得到的第一次改性后的分子筛A1与60g氧化铝粉混捏,两次焙烧温度皆为600℃,在催化剂A3中Pt和Pd含量分别为0.5wt%和0.1wt%(以催化剂质量计),其他均与实施例2相同。
实施例5
本实施例提供一种异构脱蜡催化剂A4,其制备方法与实施例2的区别仅在于:使用20g实施例1中制备得到的第一次改性后的分子筛A1与100g氧化铝粉混捏,两次焙烧温度皆为300℃,焙烧时间皆为20小时,在催化剂A4中Pt和Pd含量分别为0.1wt%和1.0wt%(以催化剂质量计),其他均与实施例2相同。
实施例6
本实施例提供一种异构脱蜡催化剂B,其制备方法与实施例2的区别仅在于:使用实施例1中制备得到的第一次改性后的分子筛B1而非A1,使用0.2mol/L CaCl2溶液而非0.1mol/L KCl溶液进行浸渍实现第二次改性,其他均与实施例2相同。
实施例7
本实施例提供一种异构脱蜡催化剂C,其制备方法与实施例2的区别仅在于:使用实施例1中制备得到的第一次改性后的分子筛C1而非A1,使用0.3mol/L SnCl2溶液而非0.1mol/L KCl溶液进行浸渍实现第二次改性,其他均与实施例2相同。
实施例8
本实施例提供一种异构脱蜡催化剂D,其制备方法与实施例2的区别仅在于:使用实施例1中制备得到的第一次改性后的分子筛D1而非A1,使用Ga(NO3)3和柠檬酸混合溶液200ml(其中,以混合溶液体积为基准,Ga(NO3)3的浓度0.1mol/L、柠檬酸的浓度为0.5mol/L)而非0.1mol/L KCl溶液进行浸渍实现第二次改性,其他均与实施例2相同。
实施例9
本实施例提供一种异构脱蜡催化剂E,其制备方法与实施例2的区别仅在于:使用实施例1中制备得到的第一次改性后的分子筛E1而非A1,使用ZnCl2和醋酸混合溶液200ml(其中,以混合溶液体积为基准,ZnCl2的浓度0.5mol/L、醋酸的浓度为0.2mol/L)而非0.1mol/L KCl溶液进行浸渍实现第二次改性,其他均与实施例2相同。
实施例10
本实施例提供一种异构脱蜡催化剂F,其制备方法与实施例2的区别仅在于:使用实施例1中制备得到的第一次改性后的分子筛F1而非A1,使用Ba(NO3)2和硝酸混合溶液200ml(其中,以混合溶液体积为基准,Ba(NO3)2的浓度0.3mol/L、硝酸的浓度为0.1mol/L)而非0.1mol/L KCl溶液进行浸渍实现第二次改性,其他均与实施例2相同。
实施例11
本实施例提供一种异构脱蜡催化剂G,其制备方法与实施例2的区别仅在于:使用实施例1中制备得到的第一次改性后的分子筛G1而非A1,使用Ba(NO3)2和硝酸混合溶液200ml(其中,以混合溶液体积为基准,Ba(NO3)2的浓度0.3mol/L、硝酸的浓度为0.1mol/L)而非0.1mol/L KCl溶液进行浸渍实现第二次改性,其他均与实施例2相同。
实施例12
本实施例提供一种异构脱蜡催化剂H,其制备方法与实施例2的区别仅在于:使用实施例1中制备得到的第一次改性后的分子筛H1而非A1,使用CuCl2和磷酸混合溶液200ml(其中,以混合溶液体积为基准,CuCl2的浓度0.5mol/L、磷酸的浓度为0.2mol/L)而非0.1mol/L KCl溶液进行浸渍实现第二次改性,其他均与实施例2相同。
实施例13
本实施例提供一种异构脱蜡催化剂I,其制备方法与实施例2的区别仅在于:使用实施例1中制备得到的第一次改性后的分子筛I1而非A1,使用MgCl2溶液和酒石酸溶液200ml(其中,以混合溶液体积为基准,MgCl2的浓度0.2mol/L、酒石酸的浓度为0.3mol/L)而非0.1mol/L KCl溶液进行浸渍实现第二次改性,其他均与实施例2相同。
实施例14
本实施例提供一种异构脱蜡催化剂J,其制备方法与实施例2的区别仅在于:使用实施例1中制备得到的第一次改性后的分子筛J1而非A1,使用BaCl2和柠檬酸混合溶液200ml(其中,以混合溶液体积为基准,BaCl2的浓度0.3mol/L、柠檬酸的浓度为0.4mol/L)而非0.1mol/L KCl溶液进行浸渍实现第二次改性,其他均与实施例2相同。
对比例1
本对比例提供一种异构脱蜡催化剂FC1,其制备方法与实施例10的区别仅在于:直接使用实施例1中MCM-22,而非第一次改性后的分子筛F1,也不进行第二次浸渍改性步骤,其他均与实施例2相同。
对比例2
本对比例提供一种异构脱蜡催化剂FC2,其制备方法与实施例10的区别仅在于:不进行第二次浸渍改性步骤,其他均与实施例7相同。
对比例3
本对比例提供一种异构脱蜡催化剂IC1,其制备方法与实施例13的区别仅在于:直接使用实施例1中ZSM-35,而非第一次改性后的分子筛I1,也不进行第二次浸渍改性步骤,其他均与实施例13相同。
对比例4
本对比例提供一种异构脱蜡催化剂IC2,其制备方法与实施例13的区别仅在于:不进行第二次浸渍改性步骤,其他均与实施例13相同。
实施例15
本实施例提供一种生产润滑油基础油的装置,该装置包括:固定床加氢反应器以及分馏系统,固定床加氢反应器包括异构脱蜡反应器(即加氢异构反应器)和与异构脱蜡反应器连接的补充精制反应器,异构脱蜡反应器与补充精制反应器通过管线连通且反应压力相同;分馏系统与补充精致反应器连接;
异构脱蜡反应器的床层分为上下两个床层,两个床层的装填体积比为1:1,床层总容积为100ml,上床层装填上述实施例提供的B催化剂,下床层装填上述实施例提供的A催化剂;异构脱蜡反应器用以实现含蜡油与氢气混合后与异构脱蜡反应器中的异构脱蜡催化剂进行异构化反应和裂化反应。
补充精制反应器用以实现异构脱蜡反应器中反应生成的产物与氢气混合后进行芳烃饱和反应;补充精制反应器中装填是中国石油的补充精制催化剂PHF-301。
分馏系统用以实现对补充精制反应器中得到的产物的分馏得到润滑油基础油。
实施例16
本实施例提供一种生产润滑油基础油的装置,该装置与实施例15的装置区别仅在于异构脱蜡反应器的上床层装填上述实施例提供的E催化剂而非B催化剂,异构脱蜡反应器的下床层装填上述实施例提供的H催化剂而非A催化剂,其他均与实施例17相同。
实施例17
本实施例提供一种生产润滑油基础油的装置,该装置与实施例15的装置区别仅在于异构脱蜡反应器的床层分为上中下三个床层而非上下两个床层,上床层、中床层和下床层的装填体积比为:3:3:4,异构脱蜡反应器的上床层装填上述实施例提供的C催化剂而非B催化剂,异构脱蜡反应器的中床层装填上述实施例提供的D催化剂,异构脱蜡反应器的下床层装填上述实施例提供的G催化剂而非A催化剂,其他均与实施例17相同。
实施例18
本实施例提供一种生产润滑油基础油的装置,该装置与实施例15的装置区别仅在于异构脱蜡反应器的上床层装填上述实施例提供的F催化剂而非B催化剂,异构脱蜡反应器的下床层装填上述实施例提供的I催化剂而非A催化剂,其他均与实施例17相同。
实施例19
本实施例提供一种生产润滑油基础油的装置,该装置与实施例15的装置区别仅在于异构脱蜡反应器的上床层装填上述实施例提供的H催化剂而非B催化剂,异构脱蜡反应器的下床层装填上述实施例提供的J催化剂而非A催化剂,其他均与实施例17相同。
对比例5
本实施例提供一种生产润滑油基础油的装置,该装置与实施例15的装置区别仅在于异构脱蜡反应器的上床层装填上述实施例提供的FC1催化剂而非B催化剂,异构脱蜡反应器的下床层装填上述实施例提供的IC1催化剂而非A催化剂,其他均与实施例17相同。
对比例6
本实施例提供一种生产润滑油基础油的装置,该装置与实施例15的装置区别仅在于异构脱蜡反应器的上床层装填上述实施例提供的FC2催化剂而非B催化剂,异构脱蜡反应器的下床层装填上述实施例提供的IC2催化剂而非A催化剂,其他均与实施例17相同。
实施例20
本实施例提供一种生产润滑油基础油的方法,该方法分别使用实施例15-实施例19提供的生产润滑油基础油的装置、对比例5-对比例6(实施例15-实施例19、对比例5-对比例6的区别仅在于异构脱蜡反应器中的催化剂种类不同)进行,具体过程如下:
1)将性质如表3所示的减压蜡油A在与氢气预混形成氢油混合物,氢油混合物进入异构脱蜡反应器,与异构脱蜡反应器中的异构脱蜡催化剂进行异构化反应和裂化反应生成油M;其中,异构脱蜡反应器的温度为380℃;
2)将油M与氢气混合在补充精制反应器中与补充精制催化剂进行芳烃饱和反应,生成的产物经分馏得到润滑油基础油;其中,补充精制反应器的温度为230℃;
相对异构脱蜡反应器的催化剂来说,反应压力为12Mpa,液时体积空速为0.7h-1,氢油体积比为700(指的是氢气与减压蜡油的体积比)。
表3减压蜡油A的性质
在上述生产润滑油基础油的方法中,分别使用实施例15-实施例19、对比例5-对比例6提供的生产润滑油基础油的装置进行润滑油基础油的生产,得到的润滑油基础油的性能如表4所示。
表4以减压蜡油A为原料的产品性质
注:液体收率计算:液体收率=液体产物收料量(重量)÷液体原料进料量(重量)×100%
基础油收率计算(基础油收率以馏出温度>320℃的组分作为基础油馏分):基础油收率=馏出温度>320℃组分重量百分比含量×液体收率
实施例21
本实施例提供一种生产润滑油基础油的方法,该方法分别使用实施例15-实施例19、对比例5-对比例6提供的生产润滑油基础油的装置(实施例15-实施例19、对比例5-对比例6的区别仅在于异构脱蜡反应器中的催化剂种类不同)进行,具体过程如下:
1)将性质如表5所示的减压蜡油B在与氢气预混形成氢油混合物,氢油混合物进入异构脱蜡反应器,与异构脱蜡反应器中的异构脱蜡催化剂进行异构化反应和裂化反应生成油M;其中,异构脱蜡反应器的温度为340℃;
2)将油M与氢气混合在补充精制反应器中与补充精制催化剂进行芳烃饱和反应,生成的产物经分馏得到润滑油基础油;其中,补充精制反应器的温度为230℃;
相对异构脱蜡反应器的催化剂来说,反应压力为15Mpa,液时体积空速为1.0h-1,氢油体积比为400(指的是氢气与减压蜡油的体积比)。
表5减压蜡油B的性质
分析项目 | 分析结果 |
密度(20℃),g/ml | 0.8438 |
馏程初馏点HK,℃ | 324 |
馏出物为50%时的气相温度即50%点50%,℃ | 453 |
馏程终馏点KK,℃ | 551 |
硫,μg/g | 32 |
氮,μg/g | 17 |
倾点,℃ | 47 |
蜡含量,ωt% | 61 |
芳烃含量,ωt% | 36.5 |
凝点,℃ | 58 |
在上述生产润滑油基础油的方法中,分别使用实施例17-实施例22提供的生产润滑油基础油的装置进行润滑油基础油的生产,得到的润滑油基础油的性能如表6所示。
表6以减压蜡油B为原料的产品性质
注:液体收率计算:液体收率=液体产物收料量(重量)÷液体原料进料量(重量)×100%
基础油收率计算(基础油收率以馏出温度>320℃的组分作为基础油馏分):基础油收率=馏出温度>320℃组分重量百分比含量*液体收率
由上述实施例可以看出,本发明提供的技术方案对于以含蜡油为原料生产润滑油基础油特别是以高凝点含蜡油为原料生产润滑油基础油表现出优异的处理能力,有效解决了目前润滑油基础油浊点高的问题;本发明提供的生产润滑油基础油的方法具有芳烃饱和性能强、加氢异构性能好、降低浊点、基础油收率高的优势,其制备得到的润滑油基础油的倾点也相对较低;本发明提供的生产润滑油基础油的方法在生产粘度和粘度指数较高且低浊点的基础油方面性能突出。
本发明提供的异构脱蜡催化剂以经过两次改性的具备十元环结构的分子筛为载体负载贵金属催化剂;使用该催化剂,通过临氢加氢异构方法,用于处理含蜡油,生产润滑油基础油,其润滑油基础油性能优异,特别时用于处理高凝点含蜡油,其制备得到的润滑油基础油兼具低浊点、低倾点、粘度高和粘度指数高的优点。
高凝点含蜡油具体性质在于,该含蜡油馏程范围为300-600℃、凝点不高于70℃,蜡含量不高于80wt%,芳烃含量不高于50wt%,硫含量不高于100μg/g,氮含量不高于50μg/g,高凝点含蜡油因馏程较重,蜡分子链长度长,蜡含量高,通过改性分子筛进行临氢加氢异构可以生产粘度大、粘度指数高的润滑油基础油。
本发明方法适用于处理减压蜡油、减压脱蜡油、加氢裂化尾油、脱沥青油、焦化蜡油,尤其适用于以重质高凝点含蜡油为原料生产低浊点、高粘度、高粘度指数的高档润滑油基础油,本发明使用效果显著,应用前景广阔。
Claims (30)
1.一种异构脱蜡催化剂的制备方法,该方法包括:
1)将含十元环结构的未成型分子筛使用改性剂进行第一次改性,经过干燥和焙烧处理得到第一次改性后的分子筛;所述第一次改性使用的改性剂包括金属盐的溶液和/或酸溶液;其中,所述金属盐包括A、/>A、/>A、/>B和/或/>B族金属盐;
2)将第一次改性后的分子筛成型后使用改性剂进行第二次改性,再经过干燥和焙烧处理得到第二次改性后的分子筛;所述第二次改性使用的改性剂包括金属盐的溶液和/或酸溶液;其中,所述金属盐包括A、/>A、/>A、/>B和/或/>B族金属盐;
3)将贵金属活性组分负载到第二次改性后的分子筛上,经干燥、焙烧得到所述异构脱蜡催化剂。
2.根据权利要求1所述的制备方法,其中,含十元环结构的未成型分子筛包括ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-22、MCM-22、NU-87、ZSM-23、ZSM-35、ZSM-48和他们复合分子筛中的一种或两种以上的组合。
3.根据权利要求1所述的制备方法,其中,所述含十元环结构的未成型分子筛具有直通孔道结构。
4.根据权利要求1所述的制备方法,其中,所述贵金属活性组分包括Pt、Pd、Ru、Rh、Re和Ir中的一种或两种以上的组合。
5.根据权利要求4所述的制备方法,其中,所述贵金属活性组分包括Pt和Pd。
6.根据权利要求5所述的制备方法,其中,在异构脱蜡催化剂中,以异构脱蜡催化剂的质量为100%计,Pt和Pd含量分别为0.3wt%和0.2wt%。
7.根据权利要求1、4、5中任一项所述的制备方法,其中,在异构脱蜡催化剂中,所述贵金属活性组分的含量占催化剂总质量为0.1-1wt%。
8.根据权利要求7所述的制备方法,其中,贵金属活性组分的含量占催化剂总质量为0.1-0.5wt%。
9.根据权利要求1所述的制备方法,其中,
在步骤1)中,所述金属盐包括钾盐、镁盐、钙盐、锶盐、钡盐、铜盐、锌盐、镓盐、锡盐中的一种或两种以上的组合;
在步骤1)中,所述酸包括硝酸、磷酸、醋酸、酒石酸、柠檬酸中的一种或两种以上的组合;
在步骤2)中,所述金属盐包括钾盐、镁盐、钙盐、锶盐、钡盐、铜盐、锌盐、镓盐、锡盐中的一种或两种以上的组合;
在步骤2)中,所述酸包括硝酸、磷酸、醋酸、酒石酸、柠檬酸中的一种或两种以上的组合。
10.根据权利要求1所述的制备方法,其中,
在步骤1)中,所述焙烧的温度为300-600℃,焙烧时间为4-10小时;
在步骤2)中,所述焙烧的温度为300-600℃,焙烧时间为5-20小时;
在步骤3)中,焙烧的温度为300-600℃,焙烧时间为4-20小时。
11. 根据权利要求1所述的制备方法,其中,所述第一次改性后的分子筛,150℃时测试B酸含量在0.2-0.6mmol/g,B酸含量:L酸含量=6:1-1:1;350℃时测试B酸含量在0.05-0.4mmol/g,B酸含量:L酸含量=6:1-1:1;其中150℃时的B酸与L酸的含量和 > 350℃时的B酸与L酸的含量和。
12.根据权利要求1所述的制备方法,其中,在步骤1)中,所述金属盐的溶液中金属盐的浓度为0.1-0.5mol/L,所述酸溶液中酸的浓度为0.1-0.5mol/L。
13.根据权利要求12所述的制备方法,其中,所述含十元环结构的未成型分子筛的质量与所述第一次改性使用的改性剂的体积之比为100g:50-70mL。
14.根据权利要求1所述的制备方法,其中,在步骤2)中,所述金属盐的溶液中金属盐的浓度为0.1-0.5mol/L,所述酸溶液中酸的浓度为0.1-0.5mol/L。
15.根据权利要求14所述的制备方法,其中,所述第一次改性后的分子筛的质量与所述第二次改性使用的改性剂的体积之比为1g:2mL。
16.权利要求1-15任一项所述的异构脱蜡催化剂的制备方法制备得到的异构脱蜡催化剂。
17.一种生产润滑油基础油的方法,其中,该方法包括:
A、含蜡油与氢气预混形成氢油混合物,氢油混合物依次与至少两种权利要求16所述的异构脱蜡催化剂进行反应,生成油M;
B、将油M与氢气混合后与补充精制催化剂进行芳烃饱和反应,生成的产物经分馏得到润滑油基础油;
含蜡油凝点不高于70℃,蜡含量不高于80wt%,芳烃含量不高于50wt%,硫含量不高于100μg/g,氮含量不高于50μg/g,含蜡油的馏程范围为300-600℃。
18.根据权利要求17所述的方法,其中,所述含蜡油为高凝点含蜡油,高凝点含蜡油的凝点不高于60℃。
19.根据权利要求17所述的方法,其中,所述补充精制催化剂的活性组分为贵金属。
20.根据权利要求19所述的方法,其中,所述补充精制催化剂的活性组分包括Pt、Pd、Ru、Rh、Re和Ir中的一种或两种以上的组合。
21.根据权利要求19所述的方法,其中,活性组分占补充精制催化剂总质量的0.1-1.0wt%。
22.根据权利要求19所述的方法,其中,补充精制催化剂的载体包括氧化铝、无定形硅铝、二氧化钛、二氧化锆和二氧化硅中的一种或两种以上的组合。
23.根据权利要求17所述的方法,其中,所述含蜡油选自减压蜡油、减压脱蜡油、加氢裂化尾油、脱沥青油、焦化蜡油中的一种或两种以上的组合。
24.根据权利要求17所述的方法,其中,
在步骤A中所述反应的温度为300-400℃、压力为8-16MPa;
在步骤B中所述芳烃饱和反应的温度为150-300℃、压力为8-16MPa。
25.根据权利要求17所述的方法,其中,
所述含蜡油凝点不高于60℃,蜡含量不高于70wt%,芳烃含量不高于50wt%,硫含量不高于100μg/g,氮含量不高于50μg/g,含蜡油的馏程初馏点不低于300℃,终馏点不高于600℃。
26.根据权利要求17所述的方法,其中,
所述含蜡油凝点不高于50℃,蜡含量不高于60wt%,芳烃含量不高于40wt%,硫含量不高于50μg/g,氮含量不高于20μg/g,含蜡油的馏程初馏点不低于320℃,终馏点不高于580℃。
27.权利要求17-26任一项所述的方法制备得到的润滑油基础油,其中,该润滑油基础油的浊点不高于-15℃。
28.根据权利要求27所述的润滑油基础油,其中,所述润滑油基础油的浊点不高于-10℃。
29.根据权利要求28所述的润滑油基础油,其中,所述润滑油基础油的浊点不高于-5℃。
30.一种生产润滑油基础油的装置,该装置包括:异构脱蜡反应器、补充精制反应器和分馏系统;其中,
异构脱蜡反应器与补充精制反应器连接,补充精制反应器与分馏系统连接;
所述异构脱蜡反应器包括至少两个床层,异构脱蜡反应器中装填至少两种异构脱蜡催化剂;所述异构脱蜡反应器用以实现含蜡油与氢气混合后与异构脱蜡反应器中的异构脱蜡催化剂进行异构化反应和裂化反应;所述至少两种异构脱蜡催化剂选自权利要求16所述的异构脱蜡催化剂;
所述补充精制反应器用以实现异构脱蜡反应器中反应生成的产物与氢气混合后进行芳烃饱和反应;
所述分馏系统用以实现对补充精制反应器中得到的产物的分馏得到润滑油基础油。
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