CN114471681A - 生产低浊点基础油的方法及催化剂、催化剂制备方法 - Google Patents
生产低浊点基础油的方法及催化剂、催化剂制备方法 Download PDFInfo
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- CN114471681A CN114471681A CN202011264518.8A CN202011264518A CN114471681A CN 114471681 A CN114471681 A CN 114471681A CN 202011264518 A CN202011264518 A CN 202011264518A CN 114471681 A CN114471681 A CN 114471681A
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- catalyst
- acid
- base oil
- cloud point
- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 239000002199 base oil Substances 0.000 title claims abstract description 112
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002253 acid Substances 0.000 claims abstract description 66
- 239000003921 oil Substances 0.000 claims abstract description 49
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 4
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- 238000000034 method Methods 0.000 claims description 28
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
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- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
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- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 10
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- 230000003197 catalytic effect Effects 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- -1 and on one hand Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 239000000843 powder Substances 0.000 description 3
- 229910000525 Si/Al2O3 Inorganic materials 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WGACMNAUEGCUHG-VYBOCCTBSA-N (2s)-2-[[(2s)-2-[[(2s)-2-acetamidopropanoyl]amino]propanoyl]amino]-n-[(2s)-6-amino-1-[[(2s)-1-[(2s)-2-[[(2s)-1-[[(2s)-5-amino-1-[[(2s)-1-[[(2s)-1-[[(2s)-6-amino-1-[[(2s)-1-amino-3-(4-hydroxyphenyl)-1-oxopropan-2-yl]amino]-1-oxohexan-2-yl]amino]-3-hydroxy- Chemical compound CC(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCCCN)C(=O)N[C@H](C(N)=O)CC1=CC=C(O)C=C1 WGACMNAUEGCUHG-VYBOCCTBSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BYMMIQCVDHHYGG-UHFFFAOYSA-N Cl.OP(O)(O)=O Chemical compound Cl.OP(O)(O)=O BYMMIQCVDHHYGG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 108010074544 myelin peptide amide-12 Proteins 0.000 description 1
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- NJFLMBDOPGVWLJ-UHFFFAOYSA-N phosphoric acid dihydrochloride Chemical compound Cl.Cl.OP(O)(O)=O NJFLMBDOPGVWLJ-UHFFFAOYSA-N 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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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
- 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
- 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
- B01J29/67—Noble metals
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- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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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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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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Abstract
本案公开一种生产低浊点基础油的方法及催化剂、催化剂制备方法,该催化剂包括载体和活性组分,所述载体包括改性分子筛,所述活性组分为贵金属;其中,所述改性分子筛是分子筛经过碱金属和/或酸改性得到的,所述分子筛具有十元环结构。本发明以高凝点含蜡油为原料,采用本发明催化剂来生产润滑油基础油,所制备基础油具有倾点、浊点低,粘度高的特点。
Description
技术领域
本发明涉及一种生产低浊点基础油的方法、用于生产低浊点基础油的催化剂、催化剂的制备方法。
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高档润滑油基础油。
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侧链的烃类,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浊点效果也有限。
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、沸点低的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的基础油分离出导致高浊点的蜡分子,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。
因此,本领域尚需对润滑油基础油的制备方法进一步进行研究。
发明内容
本发明的主要目的在于提供一种生产低浊点基础油的方法、用于生产低浊点基础油的催化剂、催化剂的制备方法,以克服现有技术中制备润滑油基础油工艺复杂,难以实施且所得润滑油基础油浊点高的问题。
为了达到上述目的,本发明提供了一种用于生产低浊点基础油的催化剂,该催化剂包括载体和活性组分,所述载体包括改性分子筛,所述活性组分为贵金属;
其中,所述改性分子筛是分子筛经过碱金属和/或酸改性助剂改性得到的,所述分子筛具有十元环结构。
本发明所述的用于生产低浊点基础油的催化剂,其中,所述改性分子筛具有直通孔道结构,所述载体还包括氧化铝。
本发明所述的用于生产低浊点基础油的催化剂,其中,所述改性分子筛150℃时B酸含量在0.1~0.6mmol/g,B酸与L酸含量之比为6:1~1:1;350℃时B酸含量在0.05~0.4mmol/g,B酸与L酸含量之比为6:1~1:1;其中150℃时B酸和L酸的总酸量>350℃时B酸和L酸的总酸量。
本发明所述的用于生产低浊点基础油的催化剂,其中,所述分子筛为ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-22、MCM-22、NU-87、ZSM-23、ZSM-35和ZSM-48中的一种或几种。
本发明所述的用于生产低浊点基础油的催化剂,其中,所述碱金属为IA或IIA族金属,所述酸为硝酸、磷酸、醋酸、酒石酸、柠檬酸、磷酸一氢酸盐或磷酸二氢酸盐;所述贵金属为Pt、Pd、Ru、Rh、Re和Ir中的一种或几种。
为了达到上述目的,本发明还提供了上述的用于生产低浊点基础油的催化剂的制备方法,包括如下步骤:
步骤1,将分子筛进行碱金属和/或酸改性;
步骤2,将步骤1得到的改性分子筛浸渍包括活性组分的浸渍液。
本发明所述的用于生产低浊点基础油的催化剂的制备方法,其中,所述步骤1的改性为将分子筛浸渍0.1~0.5mol/L的碱金属溶液和/或0.1~0.5mol/L的酸溶液。
为了达到上述目的,本发明尚提供了一种生产低浊点基础油的方法,包括:
步骤a,将原料油与氢气预混形成氢油混合物,然后通过催化剂床层,在催化剂作用下进行异构化反应和裂化反应;
其中,催化剂床层为至少两层,每层催化剂床层装填有一种权利要求1至5任一项所述的生产低浊点基础油的催化剂。
本发明所述的生产低浊点基础油的方法,其中,还包括:
步骤b,将步骤a得到的生成油与氢气混合后,在补充精制催化剂作用下进行芳烃饱和反应,生成产物进行分馏得到低浊点基础油。
本发明所述的生产低浊点基础油的方法,其中,所述原料油的馏程范围为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;所述低浊点基础油100℃运动粘度不大于13mm2/s,终馏点不大于600℃。
本发明的有益效果:
本发明提供了一种用于生产润滑油基础油的催化剂,该催化剂适用于处理减压蜡油、减压脱蜡油、加氢裂化尾油、脱沥青油和焦化蜡油,尤其适用于以重质高凝点含蜡油为原料生产低浊点高档润滑油基础油。由本发明催化剂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、降低基础油倾点、浊点性能高,尤其是生产粘度和粘度指数较高且低浊点的基础油方面性能更加优异。
具体实施方式
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。
本发明提供了一种用于生产低浊点基础油的催化剂,该催化剂包括载体和活性组分,所述载体包括改性分子筛,所述活性组分为贵金属元素;
其中,所述改性分子筛是分子筛经过碱金属和/或酸改性助剂改性得到的,所述分子筛具有十元环结构。
在一实施方式中,分子筛为ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-22、MCM-22、NU-87、ZSM-23、ZSM-35和ZSM-48中的一种或几种,即选自具有十元环结构的分子筛,具有十元环结构分子筛在异构领域表现出较好的催化性能,而且该些分子筛具有直通孔道结构。在另一实施方式中,分子筛中Si/Al2O3摩尔比为30~120,平均晶粒大小为50~100nm。
在一实施方式中,将上述分子筛进行碱金属和/或酸改性助剂得到改性分子筛。改性方式例如为浸渍方式。具体可以为将碱金属的化合物溶于水中形成浸渍液,将上述分子筛浸渍该浸渍液,得到改性分子筛;所述酸例如为酸性化合物,该改性方式具体为将酸性化合物溶于水形成浸渍液,将上述分子筛浸渍该浸渍液,得到改性分子筛。也可以为将分子筛分别浸渍碱金属化合物形成的浸渍液和酸性化合物形成的浸渍液,本申请不限定浸渍碱金属化合物和酸性化合物的先后顺序,例如可以先浸渍碱金属化合物浸渍液,再浸渍酸性化合物浸渍液;也可以先浸渍酸性化合物浸渍液,再浸渍碱金属化合物浸渍液。
在一实施方式中,碱金属选自IA和IIA族金属中一种或几种,例如可以为锂、钠、钾、铷、铯、钫、铍、镁、钙、锶、钡、镭等。碱金属化合物为可溶性碱金属盐类,如含硝酸根碱金属盐,含氯碱金属盐。酸性化合物可以为硝酸、磷酸、醋酸、酒石酸、柠檬酸、磷酸一氢酸盐和磷酸二氢酸盐中一种或几种。在另一实施方式中,碱金属化合物形成的浸渍液中,以碱金属计的浓度为0.1~0.5mol/L;酸性化合物形成的浸渍液中,以酸性化合物计的浓度为0.1~0.5mol/L。浸渍过程中每100g分子筛采用酸性化合物浸渍液或碱金属化合物浸渍液的体积为60~100ml,利用酸性化合物或碱性金属化合物对分子筛进行改性可以有效改善载体的孔结构性质和酸性分布,进而对催化剂的催化性能进行改善。
上述分子筛进行碱金属和/或酸改性得到改性分子筛,利用吡啶红外对改性分子筛进行表征,其150℃时B酸含量在0.1~0.6mmol/g,B酸:L酸=6:1~1:1;350℃时B酸含量在0.05~0.4mmol/g,B酸:L酸=6:1~1:1,其中150℃总酸量(即B酸+L酸的酸量)>350℃总酸量(即B酸+L酸的酸量)。如此,利用该种分子筛制备的催化剂,用于高凝点含蜡油的加氢异构,生产润滑油基础油,其基础油产品具有凝点高、倾点和浊点低、粘度和粘度指数较高、芳烃含量低、基础油收率高的优点。
在一实施方式中,本发明催化剂载体还包括氧化铝,如此将上述改性分子筛和氧化铝形成复合载体。本发明催化剂活性组分可以为贵金属,例如为Pt、Pd、Ru、Rh、Re和Ir中的一种或几种。在另一实施方式中,以催化剂总质量为基准,催化剂中载体含量为90~98%,活性组分含量为0.1~1%,更进一步地,载体中分子筛含量例如为30~80%,载体中氧化铝含量例如为20~70%。
本发明还提供了一种上述用于生产低浊点基础油的催化剂的制备方法,包括如下步骤:
步骤1,将分子筛进行碱金属和/或酸改性;
步骤2,将步骤1得到的改性分子筛浸渍包括活性组分的浸渍液。
上述已对分子筛类型以及改性方式等进行了详细阐述,于此不再赘述。
在一实施方式中,将步骤1得到的改性分子筛浸渍包括活性组分的浸渍液,然后干燥、焙烧等得到用于生产低浊点基础油的催化剂。在另一实施方式中,将步骤1得到的改性分子筛与氧化铝作为催化剂载体,浸渍包括活性组分的浸渍液,然后干燥、焙烧等得到用于生产低浊点基础油的催化剂。
在一实施方式中,本发明活性组分为贵金属,例如为Pt、Pd、Ru、Rh、Re和Ir中的一种或几种。本发明对包含活性组分的浸渍液的浓度不作特别限定,对浸渍活性组分的方式不作特别限定,例如为等体积浸渍等,只要使得本发明所得催化剂满足,以催化剂总质量为基准,载体含量为90~98,活性组分含量为0.1~1%,改性助剂含量为0.5~5%,更进一步地,载体中分子筛含量例如为30~80%,载体中氧化铝含量例如为20~70%。
本发明尚提供了一种生产低浊点基础油的方法,包括:
步骤a,将原料油与氢气预混形成氢油混合物,然后通过催化剂床层,在催化剂作用下进行异构化反应和裂化反应;
其中,催化剂床层为至少两层,每层催化剂床层装填有一种上述的生产低浊点基础油的催化剂。
在一实施方式中,本发明原料油选自减压蜡油、减压脱蜡油、加氢裂化尾油、脱沥青油、焦化蜡油中一种或几种;在另一实施方式中,本发明原料油馏程范围为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。
本发明对原料油与氢气混合的比例不作特别限定,例如形成饱和有氢气的原料油,通过催化剂床层进行异构化和裂化反应。本发明对反应工艺条件不作特别限定,本领域常规反应条件即可。关键的是,催化剂床层为至少两层,每一层中装填有上述制备的用于生产低浊点基础油的催化剂。本发明不特别限定催化剂的组合形式,例如两层催化剂床层为相同种类的催化剂,或者两层分别为任一上述制备的不同催化剂。
在一实施方式中,本发明生产低浊点基础油的方法还包括:步骤b,将步骤a得到的生成油与氢气混合后,在补充精制催化剂作用下进行芳烃饱和反应,生成产物进行分馏得到低浊点基础油。
本发明对步骤b中生成油与氢气的混合比例不作特别限定,按本领域常规方法即可。本发明对补充精制催化剂不作特别限定,例如为市售工业补充精制催化剂,又例如补充精制催化剂的活性组分为贵金属Pt和Pd,载体材质为氧化铝。本发明对芳烃饱和反应工艺条件和分馏条件不作特别限定,本领域常规方法即可。
如此,经过上述方法即可得到目标产品低浊点基础油,该低浊点基础油100℃运动粘度不大于13mm2/s,终馏点不大于600℃,浊点不高于-10℃,进一步地浊点不高于-7℃,更进一步地,浊点不高于-5℃。
由此,本发明提供一种用于生产低浊点基础油的催化剂,以解决现有技术制备的润滑油基础油浊点偏高的问题,尤其解决了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的问题,本发明对原料油中大分子转化能力高,可以有效的将蜡分子进行异构化,从而降低所制备的基础油的浊点。
本发明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、降低基础油倾点、浊点性能高,尤其是生产粘度和粘度指数较高且低浊点的基础油方面性能更加优异。
下面通过具体实施例对本发明技术方案做进一步说明。
实施例1
所述ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-22、MCM-22、NU-87、ZSM-23、ZSM-35、ZSM-48是市售或由任意现有方法制备,优选Si/Al2O3摩尔比30~120、平均晶粒大小为50~100nm。分子筛经过碱金属溶液或酸性溶液改性,其中碱金属选自IA或IIA族金属,酸选自硝酸、磷酸、醋酸、酒石酸、柠檬酸中一种或几种,改性的过程是将改性助剂IA或IIA族金属盐溶液浓度或上述酸溶液浓度控制0.1~0.5mol/L浸渍到分子筛上,分子筛质量(单位:g)与浸渍液体积(单位:ml)比为100:60~100,改性前分子筛原粉SiO2/Al2O3摩尔比,平均粒径以及分子筛改性试剂如表1所示,其中,表1中分子筛原粉取100g为例进行说明。
表1分子筛性质及改性试剂
表1中改性后的分子筛经过100℃干燥4小时和550℃焙烧6小时处理,用于进行吡啶红外(Py-IR)表征和制备催化剂。
样品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分子筛的Py-IR表征结果
实施例2
将实施例1中改性分子筛ZSM-5称重70g(干基重),与40g氧化铝粉(纯度为75%)混捏,经过挤条成型,湿条于100℃干燥、550℃焙烧后制备成催化剂载体。
采用等体积浸渍方法制备催化剂。将含PtCl2和PdCl2的溶液浸渍到催化剂载体上,湿条120℃干燥、550℃焙烧后制备成催化剂A,催化剂中Pt和Pd含量分别为0.3wt%和0.2wt%(以催化剂质量计)。
实施例3
与实施例2不同的在于:采用实施例1中的SAPO-11,其余都相同,制备成催化剂B。
实施例4
与实施例2不同的在于:采用实施例1中的EU-1,其余都相同,制备成催化剂C。
实施例5
与实施例2不同的在于:采用实施例1中的ITQ-13,其余都相同,制备成催化剂D。
实施例6
与实施例2不同的在于:采用实施例1中的ZSM-22,其余都相同,制备成催化剂E。
实施例7
与实施例2不同的在于:采用实施例1中的MCM-22,其余都相同,制备成催化剂F。
实施例8
与实施例2不同的在于:采用实施例1中的NU-87,其余都相同,制备成催化剂G。
实施例9
与实施例2不同的在于:采用实施例1中的ZSM-23,其余都相同,制备成催化剂H。
实施例10
与实施例2不同的在于:采用实施例1中的ZSM-35,其余都相同,制备成催化剂I。
实施例11
与实施例2不同的在于:采用实施例1中的ZSM-48,其余都相同,制备成催化剂J。
实施例12
以A和B催化剂为例,进行真实原料加氢评价反应,反应在100ml加氢固定床上进行,B催化剂装填在加氢异构反应器上部,A催化剂装填在下部,两种催化剂装填比例为1:1(按催化剂重量计),记为B/A。
实施例13
与将实施例12不同的在于:以E和H催化剂为例,E催化剂装填在加氢异构反应器上部,H催化剂装填在下部,记为E/H。
实施例14
与将实施例12不同的在于:以C、D和G催化剂为例,C催化剂装填在加氢异构反应器上部,D催化剂装填在中部,G催化剂装填在下部,三种催化剂装填比例为1:1:1(按催化剂重量计),记为C/D/G。
实施例15
与将实施例12不同的在于:以F和I催化剂为例,F催化剂装填在加氢异构反应器上部,I催化剂装填在下部,记为F/I。
实施例16
与将实施例12不同的在于:以H和J为催化剂为例,H催化剂装填在加氢异构反应器上部,I催化剂装填在下部,记为H/J。
对比例1
与实施例9不同的在于:采用实施例1中未经过改性的ZSM-23制备催化剂,其余都相同,制备成的催化剂为催化剂H1;
与实施例11不同的在于:采用实施例1中未经过改性的ZSM-48制备催化剂,其余都相同,制备成的催化剂为催化剂J1
与实施例16不同的在于:将催化剂H换成H1,将催化剂J换成催化剂J1,其余都相同。
实施例17对实施例12至实施例16及对比例1中装填的催化剂进行加氢评价,加氢评价采用两个串联反应器,一个为异构脱蜡反应器(实施例12-16以及对比例1的催化剂皆装入异构脱蜡反应器中),另一个为补充精制反应器,异构脱蜡反应器经过加氢异构后,其生成油与高纯氢气混合被送入补充精制反应器,与补充精制催化剂进行芳烃饱和反应,生成产物进入分馏系统,可得到低浊点的润滑油基础油,其中补充精制反应器中装填市售工业补充精制催化剂PHF-301,金属活性组分采用贵金属Pt和Pd,载体材质为硅铝材料。
评价原料油为加氢处理后的减压蜡油,原料油性质如表3所示。
表3原料油性质
加氢评价工况条件如表4所示,加氢评价产品经过实沸点切割,大于330℃的产品性质如表5所示。
表4加氢评价工况条件
异构脱蜡反应器温度,℃ | 375 |
反应压力,MPa | 12 |
液时体积空速,h<sup>-1</sup> | 0.85 |
氢油体积比 | 500 |
补充精制反应器温度,℃ | 225 |
表5加氢评价结果
由本发明的实施例可以看出,本发明方法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,该种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、降低基础油倾点、浊点性能高,尤其是生产粘度和粘度指数较高且低浊点的基础油方面性能更加优异。
本发明具有十元环结构的分子筛(ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-22、MCM-22、NU-87、ZSM-23、ZSM-35、ZSM-48经过碱金属和/或酸改性助剂改性得到改性分子筛,对改性分子筛进行吡啶红外表征,其150℃时B酸含量在0.1~0.6mmol/g,B酸:L酸=6:1~1:1;350℃时B酸含量在0.05~0.4mmol/g,B酸:L酸=6:1~1:1,其中150℃总酸量(B酸+L酸)>350℃总酸量(B酸+L酸),利用该种分子筛制备的催化剂,通过临氢加氢异构方法,用于处理高凝点含蜡油,生产润滑油基础油,具有倾点和浊点低、粘度和粘度指数较高、芳烃含量低、基础油收率高的优点。
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、焦化蜡油中一种或几种,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,本发明使用效果显著,应用前景广阔。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (10)
1.一种用于生产低浊点基础油的催化剂,其特征在于,该催化剂包括载体和活性组分,所述载体包括改性分子筛,所述活性组分为贵金属元素;
其中,所述改性分子筛是分子筛经过碱金属和/或酸改性得到的,所述分子筛具有十元环结构。
2.根据权利要求1所述的用于生产低浊点基础油的催化剂,其特征在于,所述改性分子筛具有直通孔道结构,所述载体还包括氧化铝。
3.根据权利要求1所述的用于生产低浊点基础油的催化剂,其特征在于,所述改性分子筛150℃时B酸含量在0.1~0.6mmol/g,B酸与L酸含量之比为6:1~1:1;350℃时B酸含量在0.05~0.4mmol/g,B酸与L酸含量之比为6:1~1:1;其中150℃时B酸和L酸的总酸量>350℃时B酸和L酸的总酸量。
4.根据权利要求1所述的用于生产低浊点基础油的催化剂,其特征在于,所述分子筛为ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-22、MCM-22、NU-87、ZSM-23、ZSM-35和ZSM-48中的一种或几种。
5.根据权利要求1所述的用于生产低浊点基础油的催化剂,其特征在于,所述碱金属为IA或IIA族金属,所述酸为硝酸、磷酸、醋酸、酒石酸、柠檬酸、磷酸一氢酸盐或磷酸二氢酸盐;所述贵金属为Pt、Pd、Ru、Rh、Re和Ir中的一种或几种。
6.权利要求1至5任一项所述的用于生产低浊点基础油的催化剂的制备方法,其特征在于,包括如下步骤:
步骤1,将分子筛进行碱金属和/或酸改性;
步骤2,将步骤1得到的改性分子筛浸渍包括活性组分的浸渍液。
7.根据权利要求6所述的用于生产低浊点基础油的催化剂的制备方法,其特征在于,所述步骤1的改性为将分子筛浸渍0.1~0.5mol/L的碱金属溶液和/或0.1~0.5mol/L的酸溶液。
8.一种生产低浊点基础油的方法,其特征在于,包括:
步骤a,将原料油与氢气预混形成氢油混合物,然后通过催化剂床层,在催化剂作用下进行异构化反应和裂化反应;
其中,催化剂床层为至少两层,每层催化剂床层装填有一种权利要求1至5任一项所述的生产低浊点基础油的催化剂。
9.根据权利要求8所述的生产低浊点基础油的方法,其特征在于,还包括:
步骤b,将步骤a得到的生成油与氢气混合后,在补充精制催化剂作用下进行芳烃饱和反应,生成产物进行分馏得到低浊点基础油。
10.根据权利要求9所述的生产低浊点基础油的方法,其特征在于,所述原料油的馏程范围为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;所述低浊点基础油100℃运动粘度不大于13mm2/s,终馏点不大于600℃。
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