CN114225943B - Waste lubricating oil debrominating agent and preparation method thereof - Google Patents
Waste lubricating oil debrominating agent and preparation method thereof Download PDFInfo
- Publication number
- CN114225943B CN114225943B CN202111608409.8A CN202111608409A CN114225943B CN 114225943 B CN114225943 B CN 114225943B CN 202111608409 A CN202111608409 A CN 202111608409A CN 114225943 B CN114225943 B CN 114225943B
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- CN
- China
- Prior art keywords
- debrominating
- agent
- hours
- debrominating agent
- lubricating oil
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 58
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 33
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 238000005507 spraying Methods 0.000 claims abstract description 24
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 239000008394 flocculating agent Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical group [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 150000002751 molybdenum Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052794 bromium Inorganic materials 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 238000007256 debromination reaction Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 4
- MKDZJIHLRSIZOV-UHFFFAOYSA-N 1,2,3-tribromo-4-phenylbenzene Chemical group BrC1=C(Br)C(Br)=CC=C1C1=CC=CC=C1 MKDZJIHLRSIZOV-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- UCTLRSWJYQTBFZ-UHFFFAOYSA-N Dehydrocholesterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)CCCC(C)C)CCC33)C)C3=CC=C21 UCTLRSWJYQTBFZ-UHFFFAOYSA-N 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910007746 Zr—O Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 0.000 description 1
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 101100342039 Halobacterium salinarum (strain ATCC 29341 / DSM 671 / R1) kdpQ gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XMYHHSMIUHHPEW-UHFFFAOYSA-N azane;molybdenum Chemical compound N.[Mo] XMYHHSMIUHHPEW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- UCTLRSWJYQTBFZ-DDPQNLDTSA-N cholesta-5,7-dien-3beta-ol Chemical compound C1[C@@H](O)CC[C@]2(C)[C@@H](CC[C@@]3([C@@H]([C@H](C)CCCC(C)C)CC[C@H]33)C)C3=CC=C21 UCTLRSWJYQTBFZ-DDPQNLDTSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- FLWXWKDFOLALOB-UHFFFAOYSA-H dysprosium(3+);trisulfate Chemical compound [Dy+3].[Dy+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FLWXWKDFOLALOB-UHFFFAOYSA-H 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8873—Zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C10G45/02—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
- C10G2300/1007—Used oils
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a waste lubricating oil debrominating agent and a preparation method thereof, which are prepared by preparing SiO containing active component Mo 2 ‑ZrO 2 And (3) spraying an isobutanol solution containing Cu-Dy in a directional manner on the ZnO composite carrier, and loading the active component Cu-Dy on the surface of the composite carrier. The debrominating agent takes the composite oxide as a carrier, can better disperse active halogen, has an ordered pore canal structure, specific pore diameter and larger pore volume, can effectively remove bromine element in waste lubricating oil, and prolongs the operation period of the subsequent waste lubricating oil hydrogenation catalyst.
Description
Technical Field
The invention relates to a waste lubricating oil debrominating agent and a preparation method thereof, belonging to the field of oil refining.
Background
During the refining process of the lubricating oil, a certain amount of additives such as tribromobiphenyl and the like are introduced, so that the Br content in the waste lubricating oil is too high. The halogen element Br has an empty d track, olefin is easy to adsorb to form a complex, and olefin in waste lubricating oil is adsorbed by a halogen center in the reaction process, so that the catalyst produces a large amount of coke, a hydrogenation catalyst pore canal is blocked, and the catalyst pore volume is reduced. The tribromobiphenyl enters a hydrofining device along with the waste lubricating oil, hydrogen bromide is generated under the action of hydrogen and a hydrogenation catalyst, the tribromobiphenyl has corrosion effect on carbon steel pipe, loss of active ingredients can be caused to a noble metal catalyst bed layer of a subsequent working section, and the service life of a noble metal catalyst is reduced, so that the debromination pretreatment of the waste lubricating oil is significant.
Patent CN 104722555a discloses a method for debrominating plastic waste, comprising the following steps: a. pretreating raw materials; b. high-temperature high-pressure debromination reaction; c. and (5) post-treatment. The following technical goals are achieved: (1) The critical pressure and critical temperature of ammonia water are far lower than those of water, the reaction condition is mild, the energy consumption is low, and the operation is easy; (2) Hydroxide dissociated from the reaction by ammonia water is used for neutralizing acidic substances generated in the reaction process, so that corrosion of reaction products to equipment is avoided; (3) The ammonium ions dissociated from the reaction by the ammonia water are used for capturing bromine generated by the reaction, so that the debromination efficiency is further improved. Patent CN101612590a discloses a method for recovering pyridine debrominating catalyst in 7-dehydrocholesterol production process. The existing recovery method has the defects of difficult operation, large environmental pollution, poor stability, low recovery rate, high production cost and the like, and restricts the large-scale industrialized production of 7-DHC. The invention is characterized in that the debrominated residue obtained by debromination is mixed with a solvent, then an activator is added, the temperature of the reaction system is raised to 60-100 ℃ for heat preservation reaction, after the reaction is finished, the filtration is carried out, the obtained filtrate is a mixture of a debromination catalyst and the solvent, and the activator is a low-boiling-point small-molecule type strong polar substance. The invention has the advantages of mild reaction condition, no pollution, good stability, high recovery rate, low production cost and the like, simplifies the operation, and is suitable for large-scale industrial production, and the byproduct sodium bromide with higher purity. The debrominating agent used for the fixed bed has no report at present aiming at the relatively higher bromine content of the waste lubricating oil, and the debrominating catalyst has a large number of mechanical pore channels, can effectively remove Br element in the waste lubricating oil, and protects the waste lubricating oil hydrogenation catalyst in the subsequent working section.
Disclosure of Invention
The invention provides a waste lubricating oil debrominating agent and a preparation method thereof, which are mainly suitable for a waste lubricating oil fixed bed hydrogenation device with higher bromine content.
The debrominating agent of the invention is a composite oxide synthesized by a silicon source, a zirconium source and a zinc source as a carrier, and Cu, mo and Dy as active components; the content of the active component of the debrominating agent is 2.8-5.8% of CuO and the content of MoO in the active component is calculated by the total mass of the debrominating agent 3 The content of Dy is 1.1-5.0% 2 O 3 The content is 0.07-0.2%.
The composite oxide synthesized by the silicon source, the zirconium source and the zinc source of the debrominating agent comprises ZrO in percentage by weight 2 The content is 2.7% -9%, the ZnO content is 8.3% -17.0%, and the rest is SiO 2 。
The specific surface area of the debrominating agent is 261-335 m 2 Per g, the pore volume is 0.80-1.2 mL/g, and the pore diameter is 16-24nm.
The preparation method of the debrominating agent comprises the following steps: uniformly mixing a certain amount of silicon source, zirconium source, zinc source, soluble molybdenum salt, surfactant and water to obtain an initial sol-gel mixture, transferring the initial sol-gel mixture into a synthesis kettle for sealing, crystallizing at 230-260 ℃ for 12-30 hours, regulating the pH value of crystal slurry to 8.5, adding a flocculating agent into the slurry for precipitation, filtering, washing, drying, extruding and molding after the reaction is finished, drying at 120-160 ℃ for 5 hours, spraying a certain amount of isobutanol solution containing Cu-Dy into a spraying device for modification of a debrominating agent, roasting at 400-480 ℃ for 2-3 hours after the spraying is finished, then introducing air containing a certain amount of water vapor, keeping constant temperature for 3 hours at 550 ℃, stopping introducing water vapor, continuing roasting at 480 ℃ in the air for 3 hours, and obtaining the waste lubricating oil debrominating agent with specific pore diameter and large pore volume and directional load of active component Cu-Mo-Dy.
The precursor of the Cu-Mo-Dy active component in the debrominating agent is chloride, sulfate, nitrate or ammonium salt thereof.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) Preparing a debrominating agent suitable for waste lubricating oil with higher bromine content, and being applicable to pretreatment of a waste lubricating oil fixed bed hydrogenation device;
（2）ZrO 2 having both acid positions of B acid and L acid and Zr 4+ Reducible, zrO 2 -SiO 2 Zr-O-Si bonds in the composite carrier form Zr-O (H) -Si bonds due to unbalanced charges, wherein the Zr-O (H) -Si bonds are new B acid centers, the B acid centers are increased, active sites for adsorbing bromine are increased, and the debromination activity of a debrominating agent is improved;
(3) The environment-friendly molybdenum-ammonia solution is used as a template agent, and the active component molybdenum is successfully embedded into the microporous catalyst precursor, so that the subsequent Cu-Mo-Dy is ensured to be used for synthesizing the active component catalyst. As molybdenum is embedded in the micropores, molybdenum atoms can be well protected when the temperature is increased, so that the molybdenum on the debrominating agent is prevented from being poisoned by Br, and meanwhile, the molybdenum activates and converts organic bromine Br adsorbed on the debrominating agent. And prevent the waste lubricating oil from cracking reaction under the action of the debrominating agent at high temperature, so as to reduce the yield of the lubricating oil;
(4) The dried composite carrier is sprayed with a certain volume of isobutanol solution containing Cu-Dy active components by a spraying device, and a debrominating agent is directionally sprayed by the spraying device, so that enrichment and positioning of the Cu-Dy active components can be formed on the surface of the carrier, the active components are ensured not to be covered in the process of adsorbing bromine in waste lubricating oil, and the debrominating agent is deactivated.
The specific embodiment is as follows:
the features of the debrominating agent, the method of preparation and its debrominating properties according to the invention are described in detail below in connection with specific embodiments, but the invention is not limited to these examples nor should it be construed as limiting the scope of the invention.
Example 1:
472.6g of silica sol (SiO 2 30 percent of (B), 27.0g of zinc chloride, 52.8g of zirconium sulfate, 27.4g of molybdenum nitrate, 5.0g of tetraethylammonium bromide and 600g of water, stirring for 6 hours, uniformly mixing to obtain an initial sol-gel mixture, transferring the initial sol-gel material into a synthesis kettle for sealing, crystallizing at 230 ℃ for 30 hours, adjusting the pH value of crystal slurry to 8.5, and after the reaction is finished, obtaining the initial sol-gel mixtureAdding flocculant into the slurry for precipitation, filtering, washing, drying, extruding and molding, drying for 5 hours at 120 ℃, spraying 660g of isobutanol solution with mass fraction of 3.9% copper chloride and 0.1% dysprosium sulfate into a spraying device for modification of a debrominating agent, roasting for 3 hours at 400 ℃ after spraying, then introducing water vapor, wherein the volume ratio of the water vapor to air is 1:10, keeping constant temperature for 3 hours at 550 ℃, stopping introducing the water vapor, and continuously roasting for 3 hours at 480 ℃ in the air to obtain the waste lubricating oil debrominating agent Cat1 with specific pore diameter and large pore volume and directional loading of active components Cu-Mo-Dy.
Example 2:
472.6g of silica sol (SiO 2 71.6g zinc sulfate, 17.2g zirconium sulfate, 7.64g molybdenum dichloride hexahydrate, 5.0g tetraethylammonium bromide and 600g water, stirring for 6h, mixing uniformly to obtain an initial sol-gel mixture, transferring the initial sol-gel material into a synthesis kettle for sealing, crystallizing at 260 ℃ for 12 h, regulating the pH value of crystal slurry to 8.5, adding a flocculating agent into the slurry for precipitation, filtering, washing, drying and extruding for forming after the reaction is finished, drying at 160 ℃ for 5h, spraying 260g of isobutanol solution with the mass fraction of 4.8% copper sulfate and 0.1% dysprosium chloride into a spraying device for modification, roasting at 480 ℃ for 2h after the spraying is finished, then introducing steam, the volume ratio of the steam to air is 1:10, then stopping introducing steam at 550 ℃ for 3h, continuing roasting at 480 ℃ for 3h, and obtaining the CaCu-Mo-Dy lubricant debrominating agent with specific pore size and high pore volume, and directionally loading active components.
Example 3:
484.6g of silica sol (SiO 2 30 percent of zinc nitrate, 57.2g of zirconium sulfate, 26.2g of molybdenum sulfate, 5.0g of tetraethylammonium bromide and 600g of water, stirring for 6 hours, mixing uniformly to obtain an initial sol-gel mixture, transferring the initial sol-gel material into a synthesis kettle for sealing, crystallizing at 240 ℃ for 18 hours, regulating the pH value of crystal slurry to 8.5, adding a flocculating agent into the slurry for precipitation, filtration, washing, drying and extrusion molding after the reaction is finished, drying at 150 ℃ for 5 hours, and spraying 360g of copper nitrate with mass fraction of 5 percent and sulfur with mass fraction of 0.1 percent into a spraying deviceModification is carried out on the debrominating agent by using the isobutanol solution of dysprosium acid, after spraying, roasting is carried out for 3 hours at 450 ℃, then water vapor is introduced, the volume ratio of the water vapor to the air is 1:10, the temperature is kept constant for 3 hours at 550 ℃, then the water vapor is stopped being introduced, and roasting is continued for 3 hours at 480 ℃ in the air, thus obtaining the waste lubricating oil debrominating agent Cat3 with specific pore diameter, larger pore volume and directional loading of the active component Cu-Mo-Dy.
Example 4:
484.6g of silica sol (SiO 2 The method comprises the steps of (1) mixing 30% of zinc nitrate, 39.6g of zirconium sulfate, 26.2g of molybdenum sulfate, 5.0g of tetraethylammonium bromide and 600g of water for 6 hours, stirring uniformly to obtain an initial sol-gel mixture, transferring the initial sol-gel material into a synthesis kettle for sealing, crystallizing at 240 ℃ for 18 hours, adjusting the pH value of crystal slurry to 8.5, adding a flocculating agent into the slurry for precipitation, filtration, washing, drying and extrusion molding after the reaction is finished, drying at 150 ℃ for 5 hours, spraying 360g of isobutanol solution with mass fraction of 5% copper nitrate and 0.1% dysprosium nitrate into a spraying device for modification of a debrominating agent, roasting at 450 ℃ for 3 hours after the spraying is finished, then introducing water vapor, wherein the volume ratio of the water vapor to air is 1:10, keeping constant temperature for 3 hours under 550 ℃, stopping introducing the water vapor, continuously roasting at 480 ℃ for 3 hours in the air, and obtaining the waste lubricating oil debrominating agent Cat4 with specific pore diameter and large pore volume and directional load of active components Cu-Mo-Dy.
The pore properties of the debrominating agent in the examples were analyzed and the analysis results are shown in Table 1.
TABLE 1 physicochemical Properties of different debrominating Agents
From table 1, it can be seen that the debrominating agents Cat 1-4 provided by the invention have larger pore diameter and pore volume through a specific preparation process.
The debrominating agent prepared in each example was packed in 30mL of a reaction tube having a height of 50mm and a bed of the debrominating agent of 27X 3.5, and the used raw oil was used as a lubricant oil, and the properties are shown in Table 2 below.
TABLE 2 Properties of used lubricating oil
| Project | Density, g/cm 3 | Bromine, μg/g |
| Waste lubricating oil | 0.89 | 232 |
And (3) digesting the sample by adopting a burning and ashing pretreatment mode, and measuring the bromine content in the synthetic oil by an ion chromatography method. 30mL of debrominating agent is taken to be filled into a fixed bed reactor, activated in the reactor, and is introduced with hydrogen, the pressure of the system is regulated to be 0.7MPa, the hydrogen amount is 50mL/min, the temperature is increased to 230 ℃ at 10 ℃/min, the temperature is kept for 2 hours, then the temperature is increased to 400 ℃ at the same temperature increasing rate, and the temperature is kept for 4 hours to enable the debrominating agent to be fully activated. After activation, heating to 230 ℃, introducing linear alkane with 0.5 percent of sulfur to inactivate the debrominating agent, then cooling to 140 ℃, pumping waste lubricating oil, and controlling the oil inlet airspeed to be 1.5h -1 The reaction temperature is 150 ℃, the reaction pressure is 7MPa, the hydrogen/oil ratio is 100:1, a debromination experiment is carried out, a sample is digested by a pre-treatment mode of burning and ashing of the product after debromination, the bromine content in the synthetic oil is measured by an ion chromatography, and the recorded reaction result is shown in Table 3.
TABLE 3 determination of debromination Activity Total bromine, μg/g
As can be seen from the data in Table 3, the catalyst for removing bromine of Cat1, cat2, cat3 and Cat4 is carried out in the raw material with the bromine content of about 232 mug/g of the waste lubricating oil, and the removal of organic bromine reaches more than 98.0%, so that the catalyst can completely meet the requirement of industrial use. The inventor also carries out 240-hour long period experiments on the debrominating agent obtained in other examples by adopting the method, and good results can be obtained, which shows that the debrominating agent has good activity and stability.
Claims (6)
1. A waste lubricating oil debrominating agent is characterized in that: the debrominating agent is a composite oxide synthesized by a silicon source, a zirconium source and a zinc source as a carrier, and Cu, mo and Dy as active components; the content of the active component of the debrominating agent is calculated by the total mass percent of the debrominating agent, and the content of CuO in the active component is 2.8-5.8 percent, moO 3 The content of Dy is 1.1-5.0% 2 O 3 The content is 0.07-0.2%;
the preparation method of the debrominating agent is characterized by comprising the following steps:
uniformly mixing a certain amount of silicon source, zirconium source, zinc source, soluble molybdenum salt, surfactant and water to obtain an initial sol-gel mixture, transferring the initial sol-gel mixture into a synthesis kettle for sealing, crystallizing at 230-260 ℃ for 12-30 hours, regulating the pH value of crystal slurry to 8.5, adding a flocculating agent into the slurry for precipitation, filtering, washing, drying, extruding and molding after the reaction is finished, drying at 120-160 ℃ for 5 hours, spraying a certain amount of isobutanol solution containing Cu-Dy into a spraying device for modification of a debrominating agent, roasting at 400-480 ℃ for 2-3 hours after the spraying is finished, then introducing air containing a certain amount of water vapor, keeping constant temperature for 3 hours at 550 ℃, stopping introducing water vapor, continuing roasting at 480 ℃ in the air for 3 hours, and obtaining the waste lubricating oil debrominating agent with the pore volume of 0.80-1.2 mL/g and the pore diameter of 16-24nm and directionally loading active components Cu-Mo-Dy.
2. The debrominating agent as claimed in claim 1, characterized in that: the composite oxide synthesized by the silicon source, the zirconium source and the zinc source comprises ZrO in percentage by weight of the composite oxide 2 The content is 2.7% -9%, the ZnO content is 8.3% -17.0%, and the rest is SiO 2 。
3. The debrominating agent as claimed in claim 1, characterized in that: the specific surface area of the debrominating agent is 261-335 m 2 /g。
4. The method for preparing a debrominating agent according to any one of claims 1 to 3, characterized in that: the preparation method of the waste lubricating oil debrominating agent comprises the following steps:
uniformly mixing a certain amount of silicon source, zirconium source, zinc source, soluble molybdenum salt, surfactant and water to obtain an initial sol-gel mixture, transferring the initial sol-gel mixture into a synthesis kettle for sealing, crystallizing at 230-260 ℃ for 12-30 hours, regulating the pH value of crystal slurry to 8.5, adding a flocculating agent into the slurry for precipitation, filtering, washing, drying, extruding and molding after the reaction is finished, drying at 120-160 ℃ for 5 hours, spraying a certain amount of isobutanol solution containing Cu-Dy into a spraying device for modification of a debrominating agent, roasting at 400-480 ℃ for 2-3 hours after the spraying is finished, then introducing air containing a certain amount of water vapor, keeping constant temperature for 3 hours at 550 ℃, stopping introducing water vapor, continuing roasting at 480 ℃ in the air for 3 hours, and obtaining the waste lubricating oil debrominating agent with the pore volume of 0.80-1.2 mL/g and the pore diameter of 16-24nm and directionally loading active components Cu-Mo-Dy.
5. The method for preparing a debrominating agent according to claim 4, wherein: the surfactant is tetraethylammonium bromide.
6. The method for preparing a debrominating agent according to claim 4, wherein: the precursor of the Cu-Mo-Dy active component is its chloride, nitrate or sulfate.
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| US5713483A (en) * | 1996-02-22 | 1998-02-03 | Naolco Chemical Corporation | Transportable brominator and a method for holding and transporting a product |
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| CN114231319A (en) * | 2021-12-02 | 2022-03-25 | 中国科学院广州能源研究所 | Method for preparing synthesis gas by co-processing waste printed circuit board and organic waste liquid |
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| FR1496433A (en) * | 1966-10-12 | 1967-09-29 | Universal Oil Prod Co | Dehalohydration catalyst and its preparation process |
| US5713483A (en) * | 1996-02-22 | 1998-02-03 | Naolco Chemical Corporation | Transportable brominator and a method for holding and transporting a product |
| JP2005350591A (en) * | 2004-06-11 | 2005-12-22 | Dai Ichi High Frequency Co Ltd | Method for debrominating plastic containing bromine compound |
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