CN114471684B - 一种生产润滑油基础油的催化剂及其载体、生产润滑油基础油的方法 - Google Patents
一种生产润滑油基础油的催化剂及其载体、生产润滑油基础油的方法 Download PDFInfo
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- CN114471684B CN114471684B CN202011257261.3A CN202011257261A CN114471684B CN 114471684 B CN114471684 B CN 114471684B CN 202011257261 A CN202011257261 A CN 202011257261A CN 114471684 B CN114471684 B CN 114471684B
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- molecular sieve
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- base oil
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 239000002199 base oil Substances 0.000 title claims abstract description 76
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 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 114
- 239000002808 molecular sieve Substances 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 230000001050 lubricating effect Effects 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 34
- 239000003921 oil Substances 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 235000011054 acetic acid Nutrition 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical group 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000002253 acid Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 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 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 241000219782 Sesbania Species 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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
- B01J29/655—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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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
- B01J29/7096—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
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- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
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- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
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- B01J2229/37—Acid treatment
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/7073—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/708—MRE-type, e.g. ZSM-48
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- B01J29/7088—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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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- 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
- B01J29/7092—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开一种生产润滑油基础油的催化剂载体,其特征在于,所述催化剂载体包含20~80wt%分子筛、10~60wt%无定形无机多孔材料、1~20wt%分子筛碎片单元和1~10wt%助剂。本发明还公开一种生产润滑油基础油的催化剂,以上述的生产润滑油基础油的催化剂载体为载体。本发明还公开一种生产润滑油基础油的方法。该方法生产出的润滑油基础油具有粘度指数高、倾点低、浊点温度低、粘度指数损失少的优点。
Description
技术领域
本发明涉及生产润滑油基础油的领域,尤其涉及一种生产润滑油基础油的催化剂及其载体,以及一种以该生产润滑油基础油的催化剂为催化剂的生产润滑油基础油的方法。
背景技术
润滑油为石油工业四大产品之一,在现代工业的发展中起着举足轻重的作用。高端润滑油生产目前主要的生产工艺有催化脱蜡和异构脱蜡等过程。其中异构脱蜡技术是国际上新出现的先进的润滑油加工工艺,它能够加工含蜡较高的原料,通过将具有很高粘度指数和较高凝点的蜡组分异构化为具有较高粘度指数和低凝点的润滑油组分,而不是将其裂化为低沸点组分,因此提高了基础油的收率,保留了粘度指数。异构脱蜡技术不仅具有很高的产品收率,而且可以获得高品质的润滑油基础油,具有很高的工业价值。
异构脱蜡是利用具有特殊孔道的分子筛的择型作用,使长链正构烷烃发生异构化反应,从而降低润滑油基础油倾点,具有基础油收率高的特点。
美国专利US7141529B2、5246566公开了利用碱金属或碱土金属对分子筛改性,调节分子筛酸量的方法来提高催化剂的选择性。
中国专利CN1448480A公开了一种以SAPO-11分子筛为主要载体的异构脱蜡催化剂的制法,通过利用有机胺对催化剂载体预处理来保留分子筛的酸性来提高催化剂的活性。
中国专利ZL201510690994.9公开了一种碱土金属同晶改性的具有TON或MTT拓扑结构的分子筛制备的载体,载体用硝酸铵、氯化铵、硫酸铵中的一种进行氨交换改性,改性后的载体用浸渍法或者离子交换法将贵金属浸渍到载体上。
中国专利ZL20151064公开一种载体包含择形裂化分子筛(ZSM-5、ZSM-8、ZSM-10、ZSM-11、ZSM-12、ZSM-35、ZSM-38和ZSM-48中的至少一种)和无定形无机多孔材料,将载体负载上贵金属后,以减压蜡油、加氢裂化尾油、沸托合成蜡、蜡膏或蜡下油中至少一种为原料,生产低倾点基础油。
中国专利CN108102698A公开一种以稀土金属(为镧、铈、镨、钷、钐等)改性的TON型分子筛与无机多孔材料复合制备成载体,然后负载贵金属制备成催化剂生产出低倾点的润滑油基础油。
在上述专利中提出了不同的催化剂载体改进方法,有的技术生产的基础油粘度指数较高、有点基础油倾点较低,但是对基础油的浊点问题都没有提及和解决。
发明内容
针对现有技术的上述问题,本发明的目的在于提供一种生产润滑油基础油的催化剂的载体以及包含该载体的生产润滑油基础油的催化剂。
本发明的目的还在于提供一种生产润滑油基础油的方法,以本发明的生产润滑油基础油的催化剂为催化剂,可以生产出倾点低、粘度指数损失少、浊点低的润滑油。
为此,本发明提供一种生产润滑油基础油的催化剂载体,所述催化剂载体包含20~80wt%分子筛、10~60wt%无定形无机多孔材料、1~20wt%分子筛碎片单元和1~10wt%助剂。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述催化剂载体包含30~70wt%分子筛。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述分子筛带有十元环结构。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述分子筛选自ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述催化剂载体包含20~40wt%无定形无机多孔材料。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述无定形无机多孔材料选自Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2或Al2O3-ZrO2中的一种或几种。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述催化剂载体包含5~15wt%分子筛碎片单元。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述分子筛碎片单元带有十元环结构。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述分子筛碎片单元由ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种制得。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述催化剂载体包含2~8wt%助剂。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述助剂为无机酸和/或有机酸。
本发明所述的生产润滑油基础油的催化剂载体,其中优选的是,所述无机酸选自硝酸、硫酸、盐酸和磷酸中一种或几种;所述有机酸选自酒石酸、柠檬酸、乙酸和乙二酸中一种或几种。
为此,本发明还提供一种生产润滑油基础油的催化剂,以上述的生产润滑油基础油的催化剂载体为载体。
为此,本发明还提供一种生产润滑油基础油的方法,以上述的生产润滑油基础油的催化剂为催化剂,原料为硫含量不高于30μg/g和氮含量不高于10μg/g的重质馏分油,所述重质馏分油为初馏点大于等于350℃的馏分油。
本发明所述的生产润滑油基础油的方法,其中优选的是,所述原料选自加氢裂化尾油、加氢处理后的减压蜡油、费托合成蜡、加氢处理后的蜡下油、加氢处理后的蜡膏中一种或几种。
本发明所述的生产润滑油基础油的方法,其中优选的是,由该方法制得的润滑油基础油的浊点不高于-12℃。
本发明所述的生产润滑油基础油的方法,其中优选的是,由该方法制得的润滑油基础油的浊点不高于-8℃。
本发明所述的生产润滑油基础油的方法,其中优选的是,由该方法制得的润滑油基础油的浊点不高于-5℃。
本案具体采取以下技术方案:
在催化剂载体中含有分子筛碎片单元,这种分子筛碎片单元具有丰富的分子筛缺陷位,而分子筛缺陷位(defect zeolite)在某些催化领域具有特殊的催化性能,在催化剂载体上引入更多具有择型催化作用的分子筛缺陷位,使得催化剂的整体催化性能得到提高,在这里需要说明,分子筛缺陷位(defect zeolite)是指在规整的分子筛结构中通过改性方法造成这种分子筛结构的不规整性。
上述分子筛碎片单元的制备方法,包括以下步骤:
步骤S1:将原料分子筛放置在酸性或碱性溶液中,充分搅拌5min~60min获得浑浊液A,其中,H+浓度不大于4mol/L,所述碱性溶液中OH-浓度不大于4mol/L;
步骤S2:将浑浊液A通过酸或碱调节至pH值为6~8,获得含有分子筛碎片结构单元的浑浊液B。
具体地,本发明催化剂载体由分子筛、无定形无机多孔材料、分子筛碎片单元和助剂构成。
其中,分子筛占催化剂载体总质量为20~80%,进一步优选30~70%;
其中,无定形无机多孔材料占催化剂载体总质量为10~60%,进一步优选为20~40%;
其中,分子筛碎片结构单元占催化剂载体总质量为1~20%,进一步优选为5~15%;
其中,助剂占占催化剂载体总质量为1~10%,进一步优选为2~8%;
其中,分子筛带有十元环结构,选自ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种;
其中,分子筛碎片单元带有十元环结构,具体来说原料分子筛选自ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中的一种或几种;
其中,制备分子筛碎片结构单元的原料分子筛与催化剂载体中分子筛相同或不同;
其中,无定形无机多孔材料选自Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2或Al2O3-ZrO2中的一种或几种;
其中,助剂为无机酸和/或有机酸,当为无机酸时,选自硝酸、硫酸、盐酸和磷酸中一种或几种;当为有机酸时,选自酒石酸、柠檬酸、乙酸、乙二酸中一种或几种。
将催化剂载体再负载上Pt、Pd、Ru、Rh、Ir中一种或者几种贵金属后,制备得到催化剂,将该种催化剂应用在生产润滑油基础油,生产基础油的原料为硫含量不高于30μg/g和氮含量不高于10μg/g的重质馏分油,其中重质馏分油为初馏点大于等于350℃的馏分油,重质馏分油优选为经过加氢处理后的减压蜡油、加氢裂化尾油、费托合成蜡、加氢处理后的蜡下油、加氢处理后的蜡膏中一种或几种混合。
所生产的润滑油基础油浊点不高于-12℃,优选为-8℃,进一步优选为-5℃。
本发明的有益效果:
本发明的生产润滑油基础油的催化剂载体中含有带有十元环结构的分子筛碎片结构单元,这种分子筛碎片结构单元因为含有大量的缺陷位,在与具有十元环结构的分子筛、无定形无机多孔材料和助剂复合制备成载体后,具有特殊的择型催化性能,这种载体制备成催化剂后应用在生产润滑油基础油领域,生产出的润滑油基础油具有粘度指数高、倾点低、浊点温度低、粘度指数损失少的优点。
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。
本发明提供的生产润滑油基础油的催化剂载体,所述催化剂载体包含20~80wt%分子筛、10~60wt%无定形无机多孔材料、1~20wt%分子筛碎片单元和1~10wt%助剂。
在一些实施例中,所述催化剂载体包含30~70wt%分子筛。
在一些实施例中,所述分子筛带有十元环结构。
在一些实施例中,所述分子筛选自ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种。
在一些实施例中,所述催化剂载体包含20~40wt%无定形无机多孔材料。
在一些实施例中,所述无定形无机多孔材料选自Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2或Al2O3-ZrO2中的一种或几种。
在一些实施例中,所述催化剂载体包含5~15wt%分子筛碎片单元。
在一些实施例中,所述分子筛碎片单元带有十元环结构。
在一些实施例中,所述分子筛碎片单元由ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种制得。
在一些实施例中,所述催化剂载体包含2~8wt%助剂。
在一些实施例中,所述助剂为无机酸和/或有机酸。
在一些实施例中,所述无机酸选自硝酸、硫酸、盐酸和磷酸中一种或几种;所述有机酸选自酒石酸、柠檬酸、乙酸和乙二酸中一种或几种。
本发明提供的生产润滑油基础油的催化剂,以上述的生产润滑油基础油的催化剂载体为载体。
本发明提供的生产润滑油基础油的方法,以上述的生产润滑油基础油的催化剂为催化剂,原料为硫含量不高于30μg/g和氮含量不高于10μg/g的重质馏分油,所述重质馏分油为初馏点大于等于350℃的馏分油。
在一些实施例中,所述原料选自加氢裂化尾油、加氢处理后的减压蜡油、费托合成蜡、加氢处理后的蜡下油、加氢处理后的蜡膏中一种或几种。
在一些实施例中,由该方法制得的润滑油基础油的浊点不高于-12℃。
在一些实施例中,由该方法制得的润滑油基础油的浊点不高于-8℃。
在一些实施例中,由该方法制得的润滑油基础油的浊点不高于-5℃。
在催化剂载体制备过程中使用到粘结剂田菁粉,该种粉末在焙烧过程中会完全分解。
实施例1
以制备100g催化剂载体为例。
本实施例中使用分子筛为市售ZSM-35分子筛。使用的无定形无机多孔材料为Al2O3和SiO2,助剂为磷酸和乙酸。
制备分子筛碎片结构单元的分子筛与载体成型所使用的分子筛相同,都是ZSM-35分子筛。
制备ZSM-35分子筛碎片单元:取ZSM-35分子筛20g放置于30ml含1mol/L盐酸溶液中,在60℃的水浴中充分搅拌30min获得浑浊液A;步骤B:将浑浊液A通过3mol/L氨水调节至pH值为6~8获得含有ZSM-35分子筛碎片单元的浑浊液B。
载体成型步骤:取ZSM-35分子筛20g、30g Al2O3、30g SiO2和10g田菁粉为在容器中进行机械混匀,将浑浊液B与5g磷酸和5g乙酸和20ml去离子水配制成浑浊液,然后滴加入到上述机械混匀的粉末中,进行混捏然后挤压成条型、均化20min,再200℃干燥1小时,550℃焙烧6小时得到催化剂载体Z1。
实施例2
以制备100g催化剂载体为例。
本实施例中使用市售分子筛ZSM-5和ZSM-48。使用的无定形无机多孔材料为Al2O3-TiO2和ZrO2,助剂为硝酸和柠檬酸。
制备分子筛碎片结构单元的分子筛为ZSM-5,与载体成型所使用的分子筛为ZSM-48。
制备ZSM-5分子筛碎片结构单元:取ZSM-5型分子筛1g放置10ml含1mol/L硫酸溶液中,在40℃的水浴中充分搅拌10min获得浑浊液A;步骤B:将浑浊液A通过2mol/L氨水调节至pH值为6~8获得含有ZSM-5型分子筛碎片结构单元的浑浊液B。
载体成型步骤:取ZSM-48型分子筛80g、8g Al2O3-SiO2、2g TiO2和10g田菁粉在容器中进行机械混匀,将浑浊液B与5g硝酸和4g柠檬酸和45ml去离子配制成浑浊液,滴加到上述机械混匀的粉末中,进行混捏然后挤压成条型、均化30min,再200℃干燥1小时,550℃焙烧6小时得到含有催化剂载体Z2。
实施例3
以制备100g催化剂载体为例。
本实施例中使用分子筛为市售MCM-22和SAPO-11分子筛。使用的无定形无机多孔材料为Al2O3-SiO2和TiO2,助剂为酒石酸和乙二酸。
制备分子筛碎片结构单元的分子筛为MCM-22与载体成型所使用的分子筛为SAPO-11。
制备MCM-22分子筛碎片结构单元:取MCM-22分子筛10g放置20ml含3mol/L氨水溶液中,在80℃的水浴中充分搅拌30min获得浑浊液A;步骤B:将浑浊液A通过1mol/L磷酸调节至pH值为6~8获得含有MCM-22分子筛碎片结构单元的浑浊液B。
载体成型步骤:取SAPO-11分子筛70g、5g Al2O3-SiO2、5g TiO2和10g田菁粉在容器中进行机械混匀,将浑浊液B与5g酒石酸和5g乙二酸与25ml去离子水配制成浑浊液,滴加入上述机械混匀的粉末中,进行混捏然后挤压成条型、均化60min、再200℃干燥1小时,550℃焙烧6小时得到催化剂载体Z3。
实施例4
以制备100g催化剂载体为例。
本实施例中使用分子筛为市售ZSM-23分子筛。使用的无定形无机多孔材料为Al2O3-ZrO2和ZrO2,助剂为磷酸和乙酸。
制备分子筛碎片结构单元的分子筛与载体成型所使用的分子筛都为ZSM-23。
制备ZSM-23分子筛碎片结构单元:取ZSM-23分子筛5g放置于20ml含2mol/L乙酸溶液中,在60℃的水浴中充分搅拌40min获得浑浊液A;步骤B:将浑浊液A通过3mol/L氨水调节至pH值为6~8获得含有ZSM-23分子筛碎片结构单元的溶液B。
载体成型步骤:取ZSM-23分子筛70g、20g Al2O3-ZrO2、10g ZrO2和10g田菁粉为在容器中进行机械混匀,将浑浊液B与3g磷酸、2g乙酸和25ml去离子水配制成浑浊液,滴加入上述机械混匀的粉末中,进行混捏然后挤压成条型、均化30min,干燥和焙烧得到载体Z4。
实施例5
本实施例中使用分子筛为市售EU-1和ZSM-22分子筛。使用的无定形无机多孔材料为Al2O3和ZrO2,助剂为硝酸。
制备分子筛碎片结构单元的分子筛为EU-1,载体成型所使用的分子筛都为ZSM-22。
制备EU-1分子筛碎片结构单元:取EU-1分子筛15g放置30ml含1mol/L盐酸溶液中,在40℃的水浴中充分搅拌20min获得浑浊液A;步骤B:将浑浊液A通过2mol/L氨水调节至pH值为6~8获得含有ZSM-22分子筛碎片结构单元的浑浊液B。
载体成型步骤:取ZSM-22分子筛40g、30g Al2O3、10g ZrO2和10g田菁粉在容器中进行机械混匀,将浑浊液B与5g硝酸和20ml去离子水配制成浑浊液,滴加入上述机械混匀的粉末中,均化40min、进行混捏然后挤压成条型、再200℃干燥1小时,550℃焙烧6小时得到载体Z5。
对比例1
与实施例4区别在于,没有分子筛碎片结构单元制备步骤,而是将制备分子筛碎片结构单元的原料直接加入载体成型步骤,具体实施方式是:取ZSM-23型分子筛75g、20gAl2O3-ZrO2、10g ZrO2和10g田菁粉为在容器中进行机械混匀,将80ml去离子水滴加入上述机械混匀的粉末中,进行混捏然后挤压成条型、均化30min,再200℃干燥1小时,550℃焙烧6小时得到催化剂载体B4。
对比例2
与实施例5区别在于,没有分子筛碎片结构单元制备步骤,而是将制备分子筛碎片结构单元的原料直接加入载体成型步骤,具体实施方式是:取EU-1分子筛15g、ZSM-22分子筛40g、30g Al2O3、10g ZrO2和10g田菁粉在容器中进行机械混匀,将80ml去离子水滴加入上述机械混匀的粉末中,均化40min、进行混捏然后挤压成条型、再200℃干燥1小时,550℃焙烧6小时得到载体B5。
实施例6
取制备的载体Z4、Z5、B4和B5各50g,通过等体积浸渍方法,将34ml含氯铂酸和氯化钯溶液浸渍到载体上,制备获得催化剂ZC3、ZC4、ZC5、BC4和BC5,各催化剂上Pt含量均为0.3%,Pd含量均为0.2%,将制备的催化剂应用在生产润滑油基础油的加氢异构领域,以经过加氢处理的减压蜡油为原料(原料性质列于表1),反应条件:反应温度360℃、氢分压12MPa、氢油体积比:500:1、体积空速0.8h-1,评价结果列于表2。
表1原料油性质
密度(20℃),g/ml | 0.8986 |
馏程 | |
HK,℃ | 318 |
50%,℃ | 425 |
KK,℃ | 518 |
硫,μg/g | 24 |
氮,μg/g | 7 |
黏度(100℃),mm2/s | 8.8 |
粘度指数 | 135 |
芳烃含量,ω% | 12.6 |
凝点,℃ | 6 |
倾点,℃ | 2 |
评价装置运转200小时后取样,经过实沸点切割后大于350℃馏分段,分析结果于表2所示。
表2评价结果
由表2的评价结果看,相比于不引入分子筛碎片结构单元的载体制备的催化剂,本发明载体制备的催化剂应用于生产润滑油基础油具有较好的浊点解决能力,浊点温度更低,同时生产的基础油凝点和倾点温度更低,基础油的粘度高、粘度指数损失少(原料粘度指数135,产品在122~129之间)、同时基础油总收率高、基础油产品中芳烃含量低。本发明制备的催化剂载体类型多样,可以应用在不同的择型催化领域,市场应用前景广。
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的保护范围。
Claims (12)
1.一种生产润滑油基础油的催化剂载体,其特征在于,所述催化剂载体通过分子筛、无定形无机多孔材料、分子筛碎片单元和助剂复合制备而成,各组分及含量如下:20~80 wt%分子筛、10~60 wt%无定形无机多孔材料、1~20 wt%分子筛碎片单元和1~10 wt%助剂;
所述分子筛带有十元环结构;
所述分子筛选自ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种;
所述分子筛碎片单元的制备方法,包括以下步骤:
步骤S1:将原料分子筛放置在酸性或碱性溶液中,充分搅拌5min~60min获得浑浊液A;
步骤S2:将浑浊液A通过酸或碱调节至pH值为6~8,获得含有分子筛碎片单元的浑浊液B;
所述碱性溶液为氨水溶液;
所述酸性溶液中的酸选自硫酸、盐酸和乙酸中的一种或几种;
所述分子筛碎片单元带有十元环结构;
所述分子筛碎片单元由ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种制得;
所述助剂为无机酸和/或有机酸。
2.根据权利要求1所述的生产润滑油基础油的催化剂载体,其特征在于,所述无定形无机多孔材料为20~60 wt%。
3.根据权利要求1所述的生产润滑油基础油的催化剂载体,其特征在于,所述无定形无机多孔材料选自Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2或Al2O3-ZrO2中的一种或几种。
4.根据权利要求1所述的生产润滑油基础油的催化剂载体,其特征在于,所述分子筛碎片单元为5~15 wt%。
5.根据权利要求1所述的生产润滑油基础油的催化剂载体,其特征在于,所述助剂为2~8 wt%。
6.根据权利要求1所述的生产润滑油基础油的催化剂载体,其特征在于,所述无机酸选自硝酸、硫酸、盐酸和磷酸中一种或几种;所述有机酸选自酒石酸、柠檬酸、乙酸和乙二酸中一种或几种。
7.一种生产润滑油基础油的催化剂,其特征在于,以权利要求1-6任一项所述的生产润滑油基础油的催化剂载体为载体。
8.一种生产润滑油基础油的方法,其特征在于,以权利要求7所述的生产润滑油基础油的催化剂为催化剂,原料为硫含量大于等于24μg/g且不高于30μg/g和氮含量大于等于7μg/g且不高于10μg/g的重质馏分油,所述重质馏分油为初馏点大于等于350℃的馏分油。
9.根据权利要求8所述的生产润滑油基础油的方法,其特征在于,所述原料选自加氢裂化尾油、加氢处理后的减压蜡油、费托合成蜡、加氢处理后的蜡下油、加氢处理后的蜡膏中一种或几种。
10.根据权利要求8所述的生产润滑油基础油的方法,其特征在于,由该方法制得的润滑油基础油的浊点不高于-12℃。
11.根据权利要求8所述的生产润滑油基础油的方法,其特征在于,由该方法制得的润滑油基础油的浊点不高于-8℃。
12.根据权利要求8所述的生产润滑油基础油的方法,其特征在于,由该方法制得的润滑油基础油的浊点不高于-5℃。
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