CN117138804A - Olefin removal catalyst capable of completely replacing clay and preparation method thereof - Google Patents
Olefin removal catalyst capable of completely replacing clay and preparation method thereof Download PDFInfo
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- CN117138804A CN117138804A CN202210562658.6A CN202210562658A CN117138804A CN 117138804 A CN117138804 A CN 117138804A CN 202210562658 A CN202210562658 A CN 202210562658A CN 117138804 A CN117138804 A CN 117138804A
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- catalyst
- nickel
- palladium
- reformate
- oil
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000004927 clay Substances 0.000 title abstract description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- ZVHHIDVFSYXCEW-UHFFFAOYSA-L nickel(ii) nitrite Chemical compound [Ni+2].[O-]N=O.[O-]N=O ZVHHIDVFSYXCEW-UHFFFAOYSA-L 0.000 claims description 2
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 239000002808 molecular sieve Substances 0.000 abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000001356 surgical procedure Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000002407 reforming Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 210000003278 egg shell Anatomy 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 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
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- -1 aluminum alkoxide Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- C10G45/10—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 platinum group metals or compounds thereof
-
- 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
- C10G2300/1088—Olefins
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Abstract
A green dealkenation catalyst for completely replacing clay contains at least one VIII group metal containing nickel and/or palladium, and the specific surface area of the carrier or catalyst is 80-300 m 2 Per gram, the pore volume is 0.40-1.0 mL/g. The catalyst is used for hydrofining the reformed oil, and can effectively remove olefin in the reformed oil. At the reaction temperature of 50-300 ℃, the pressure of 0.5-3.0 MPa and the weight airspeed of 0.5-30.0 h ‑1 The olefin removal rate is more than 98 percent under the condition that the hydrogen-oil volume ratio is 2-100, the bromine index of the product is less than 20mg Br/100g oil, and the aromatic hydrocarbon loss is less than 0.1wt%. The catalyst of the invention has simple and environment-friendly startup process, and completely replaces non-hydro-olefin removal technologies such as clay, molecular sieve and the likeAnd (5) performing surgery.
Description
Technical Field
The invention relates to an efficient environment-friendly catalyst for removing olefins to completely replace clay and a preparation method thereof. In particular to a hydrofining catalyst for reforming generated oil by taking nickel palladium as an active component and a preparation method thereof.
Background
Light aromatic hydrocarbons such as benzene, toluene and xylene (BTX) are important organic chemical raw materials, and mainly originate from catalytic reforming reactions of naphtha. The reformate is rich in aromatic hydrocarbons and contains a small amount of olefins. Due to the relatively active nature of olefins, particularly trace amounts of diolefins, there are varying degrees of impact on the performance of the aromatics extraction and downstream equipment, xylenes (PX) adsorbents, and catalysts in the aromatics complex. As the processing materials of the reforming device become more complex and diversified (particularly heavy and poor), the processing severity of the reforming device becomes higher and higher, and the content of olefins in the reformed oil also tends to be obviously increased. Therefore, the pressure of the aromatic refining process is increasing, and most devices still adopt the traditional industrial granular clay olefin removal process, so that the process is difficult to adapt to the change, and particularly for the C8+ mixed aromatic hydrocarbon fraction, clay replacement frequency is higher and higher due to the fact that the aromatic hydrocarbon fraction is rich in indane, colloid and other heavy components which are easy to deactivate clay. Some enterprises use granular clay which needs to be replaced even once a week, so that the labor intensity is very high, and the clay consumption is also very high. The abandoned clay contains a certain amount of heavy aromatic hydrocarbon, the landfill or burning treatment can bring serious pollution to the environment, and the post-treatment cost is high, so that the comprehensive utilization cost of the clay is high.
In recent years, there are also methods for non-hydrogenation catalytic olefin removal using a catalyst containing molecular sieve, which have a service life longer than that of granular clay, but which still have environmental problems such as relatively short single-pass service life, need for continuous catalyst removal regeneration and post-treatment landfill. In addition, because the reaction mechanisms of the granular clay and the refined catalyst containing the molecular sieve are basically similar, the alkylation, superposition, condensation and other reactions are mainly carried out to remove olefin, so that the content of heavy aromatic hydrocarbon with low utilization value in the reaction product is increased, and the dry point of the reaction product is increased. Therefore, there is an urgent need for an environmentally friendly dealkenation catalyst to completely replace the industrial granular clay and molecular sieve-containing refined catalyst.
The other method for removing olefin mainly adopts a selective hydrogenation process, which is to selectively hydrogenate olefin in the reformed oil or raffinate oil under the hydrogenation condition, and realize deep mild hydrogenation to remove olefin in the aromatic hydrocarbon under the condition that the aromatic hydrocarbon is not saturated by hydrogenation. Unlike clay and molecular sieve-containing catalyst, the hydrogenation process is adopted to eliminate olefin and the dry point of the reaction product is not raised. One is a method for catalyzing and hydrogenating by adopting a catalyst containing non-noble metal (such as Co-Mo or Ni-Mo), which needs a higher reaction temperature (280-320 ℃) and a lower volume space velocity (1-2 h) -1 ) The aromatic hydrocarbon loss is large, the catalyst life is short, regeneration or replacement is needed for several months, and the process and the catalyst are eliminated at present. The other is a low-temperature hydrogenation process adopting a noble metal (Pd and Pt) hydrofining catalyst, the reaction severity is lower, the reaction temperature is 120-170 ℃, the reaction pressure is 1.0-2.4 MPa, the aromatic hydrocarbon loss is less than 0.5wt%, and the catalyst can stably run for a long period. The deactivated catalyst is regenerated by adopting an external regeneration mode, and noble metals such as Pd, pt and the like of the waste catalyst can be entrusted to the recovery enterprises with hazardous waste treatment qualification for high-efficiency recovery. The selective hydrogenation process can be divided into a common trickle bed hydrogenation process and a liquid phase hydrogenation process, wherein the trickle bed hydrogenation process adopts a conventional process flow, the liquid phase hydrogenation process adopts an inlaid process flow, and a hydrogenation reaction module is inlaid at the feeding or bottom of a reforming depentanizer, so that the purpose of olefin removal can be achieved by supplementing a small amount of hydrogen. From the comprehensive consideration of long-term investment, long-term stable operation, economic and social benefits, environmental protection and the like, the adoption of the reforming generated oil liquid-phase hydrogenation olefin removal process and catalyst is a necessary trend of future development.
CN1448474a discloses a selective hydrodeolefination catalyst for reformate. The catalyst contains 0.1-1.0 wt% of noble metal active component, 0.05-0.50 wt%The alkali metal or alkaline earth metal is used as an auxiliary agent, and the catalyst carrier is a refractory inorganic oxide. The surface area of the catalyst is 150-250 m 2 Per gram, the pore volume is 0.3-0.8 mL/g. The invention is used for selectively hydrodeolefine in the gasoline fraction reforming generated oil, and the reaction temperature is 150-250 ℃, the pressure is 1.5-3.0 MPa, and the volume airspeed is 2.0-4.0 h -1 Under the condition that the bromine index of the product is less than 100mgBr/100g of oil, the aromatic hydrocarbon loss is 0.5wt%. However, the catalyst of the invention cannot completely replace clay, and the aromatic hydrocarbon loss is large.
CN104014337a discloses a catalyst for selectively hydrodeolefine of reforming oil, which comprises active component oxide, auxiliary oxide and carrier, wherein the mass percentage of the active component oxide is 0.05-0.5 wt% and the mass percentage of the auxiliary oxide is 0.5-10 wt% calculated by metal, the rest is carrier; the active component oxide is at least one of noble metal Pt, pd and Ru oxides, the auxiliary oxide is one or two of Na, K, mg, ca, co, fe, ni, mo, cu oxides, and the carrier is Al 2 O 3 . The catalyst has the following characteristics: the noble metal is distributed on the carrier in a thin eggshell shape, and the eggshell thickness is 0.37-1 mm; the specific surface area of the catalyst is 250-400 m 2 /g; pore volume of 0.2-1.2 cm 3 And/g, wherein the pores with the pore diameters of 5-50 nm account for 50-80% of the total pore channels of the catalyst. The catalyst of the invention can not completely replace clay, and the noble metal utilization rate is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a hydrofining catalyst for reforming generated oil by taking nickel palladium as a main active component and a preparation method thereof. The catalyst is used for hydrofining of the reformed oil, can efficiently remove olefin in the reformed oil to completely replace industrial granular clay or molecular sieve catalyst, has less than 0.1w% of aromatic hydrocarbon loss, and has simple and environment-friendly startup process.
The catalyst is characterized by comprising an alumina carrier containing sulfate radicals, a main active component, an auxiliary agent and optional halogen, wherein the main active component is nickel, and the auxiliary agent is VIII metal at least containing palladium.
The price of noble metal Pt, pd, rh, ru, especially Rh and Pd, has been on the rise, and it is critical how to increase the metal utilization and reduce the disposable investment cost. Based on the full research, ni with relatively low price is preferably selected as a main active component, and a proper amount of Pd is used as an auxiliary agent, so that the utilization rate of metal is fully improved, the dealkenation reaction performance of the catalyst is ensured, and the price of the catalyst is reduced.
More importantly, through long-term research, nickel is selected as a main active component and at least palladium-containing VIII metal is selected as an auxiliary agent, and an alumina carrier containing sulfate radicals is used as an auxiliary agent, so that the obtained catalyst does not need to be presulfided before being used, and unexpected technical effects are obtained.
According to the dealkenation catalyst for completely replacing clay, the auxiliary agent is palladium or a combination of palladium and platinum.
The dealkenation catalyst for completely replacing clay provided by the invention comprises an alumina carrier containing sulfate radicals, a main active component nickel, an auxiliary agent containing at least palladium VIII group metal and halogen. Wherein the content of the main active component nickel in the catalyst is 3-20wt%, preferably 5-15wt%, the content of the auxiliary agent is 0.05-0.5wt%, preferably 0.1-0.3wt%, the mass ratio of the main active component and the auxiliary agent is 15-50, the halogen content is 0.2-3wt%, preferably 0.6-2wt%, and the content of the elemental sulfur is 0.03-1wt%, preferably 0.1-0.5wt%, based on the weight of the carrier.
The carrier of the catalyst is aluminum hydroxide powder containing a certain amount of sulfate radical obtained by taking sodium metaaluminate and aluminum sulfate as raw materials through precipitation, aging and washing, and then the alumina carrier containing the sulfate radical is obtained through molding, roasting and modification.
The catalyst is prepared by taking alumina containing a certain amount of sulfate radical as a carrier and loading active components, is used for hydrofining of the reformed oil, can effectively remove olefin in the reformed oil, has bromine index of less than 20mg Br/100g oil and aromatic hydrocarbon loss of less than 0.1wt%.
Detailed Description
The present invention will be described in further detail by way of examples. The features and advantages of the present invention will become more apparent from the description. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
In addition, the technical features described below in the different embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The invention prepares gamma-alumina carrier by extrusion molding, drying and roasting pseudo-boehmite powder (aluminum hydroxide powder) synthesized by adopting sodium metaaluminate and aluminum sulfate neutralization precipitation method, the catalyst prepared by loading active components is used for hydrofining of reformed oil, olefin in the reformed oil can be effectively removed, the olefin removal rate is more than 98%, the bromine index of the product is less than 20mg Br/100g oil, and the aromatic hydrocarbon loss is less than 0.1wt%. The alumina carrier used in the invention contains a certain amount of sulfate radical, although not wishing to be limited by theory, the existence of the sulfate radical is favorable for generating hydrogen sulfide in situ at high temperature, proper sulfuration is carried out on metal components of the catalyst, the hydrogenolysis activity of excessive metal and the aromatic hydrocarbon saturation hydrogenation activity of the catalyst are inhibited, thereby reducing the aromatic hydrocarbon loss, and the catalyst operation method is simple, safe and environment-friendly. The traditional method is to adopt the mode of injecting sulfur-containing compounds such as dimethyl disulfide and the like to carry out vulcanization on site when the catalyst is opened, so that the vulcanization process flow is set, the subsequent flow is polluted, the starting method is complex, and the environment is not protected.
According to an embodiment of the present invention, there is provided a catalyst for removing olefins from reformate, which is capable of completely replacing clay, and is characterized in that the catalyst comprises an alumina carrier containing sulfate, a main active component, an auxiliary agent and optionally halogen, wherein the main active component is nickel, and the auxiliary agent is VIII metal containing at least palladium.
According to an exemplary embodiment of the present invention, the catalyst of the present invention preferably comprises an alumina support containing sulfate, a primary active component of nickel, an adjunct of a group viii metal containing at least palladium, and a halogen. Wherein, based on the weight of the carrier, the content of the main active component nickel in the catalyst is 3 to 20wt%, preferably 5 to 15wt%, the content of the auxiliary agent is 0.05 to 0.5wt%, preferably 0.1 to 0.3wt%, the halogen content is 0.2 to 3wt%, preferably 0.6 to 2wt%, and the content of the elemental sulfur is 0.03 to 1wt%, preferably 0.1 to 0.5wt%.
According to an exemplary embodiment of the invention, the promoter is preferably palladium or a combination of palladium and platinum.
According to an exemplary embodiment of the invention, the halogen is preferably chlorine. While not wishing to be bound by theory, the presence of the halogen helps to provide some acidity to the catalyst and can help to ensure that dispersion of the metal is provided during catalyst preparation.
According to an exemplary embodiment of the present invention, the present invention further provides a method for preparing a sulfate-containing alumina carrier and a catalyst, comprising the steps of:
a) The aluminum hydroxide powder used for preparing the alumina carrier containing sulfate radical is prepared by the reaction of sodium metaaluminate and aluminum sulfate precipitation method;
b) Roasting aluminum hydroxide powder at 400-1000 ℃ after forming, and then treating the aluminum hydroxide powder for 0.5-12 hours at 300-800 ℃ by using saturated/supersaturated water vapor at 100-150 ℃ to obtain an alumina carrier containing sulfate radicals, wherein the amount of water vapor passing through the carrier is 0.2-10 times of the weight of the carrier;
c) Contacting the support obtained in b) with an aqueous precursor solution comprising halogen, nickel and at least a group viii metal containing palladium to obtain a catalyst precursor;
d) Drying the catalyst precursor obtained in c) at 60-200 ℃ for 6-12 hours, activating for 2-6 hours at 400-650 ℃ in air atmosphere, and finally reducing for 2-6 hours at 450-550 ℃ in hydrogen atmosphere.
In the above preparation method, step c) is to introduce the catalyst active component for impregnation, and the impregnation may be a method of partial impregnation and co-impregnation, and a method of saturated impregnation or supersaturation impregnation. The liquid/solid volume ratio of the impregnating liquid to the carrier at the time of impregnation is 0.5 to 4.0, preferably 1.0 to 2.0. Suitable impregnation temperatures are from 15 to 60℃and preferably from 20 to 30 ℃. The impregnation fluid should also be formulated to contain a halogen acid, preferably hydrochloric acid, to introduce the halogen component and to provide for a uniform distribution of the metal component throughout the support. Excess impregnating solution after supersaturation is removed by filtration or evaporation of the solvent in vacuo. The method for evaporating the solvent in vacuum can be carried out by adopting a rotary vacuum evaporator, and the specific operation method comprises the following steps: preparing a water-soluble compound containing each component into an impregnating solution, impregnating an alumina carrier under the conditions of 0.001-0.10 MPa and rotation, wherein the liquid/solid volume ratio of the impregnating solution to the carrier is 1.1-3.0, the rotation linear speed is 0.01-2.0 m/s, and drying and roasting activation are carried out after the impregnation. The pressure of vacuum rotary impregnation is preferably 0.001 to 0.08MPa. The heating is performed while the impregnation is performed, and the heating temperature, that is, the impregnation temperature is preferably 20 to 90 ℃, more preferably 50 to 80 ℃, and the rotation speed is preferably not too high, and the preferred linear rotation speed is 0.02 to 0.8 m/s, more preferably 0.05 to 0.5 m/s. The impregnation time is preferably 1 to 8 hours, more preferably 2 to 4 hours. After vacuum rotary impregnation, the moisture in the impregnation liquid is basically evaporated, and the catalyst is in a dry state, and the carrier can be directly taken out for drying and roasting activation.
In an exemplary embodiment of the present invention, the nickel-containing precursor used to formulate the impregnating solution includes, but is not limited to, one or more of nickel chloride, nickel nitrate, nickel acetate, nickel carbonate, nickel sulfate, nickel hydroxide, nickel formate, nickel acetate, nickel nitrite. Precursors for preparing the impregnating solution that contain at least a group viii metal containing palladium include, but are not limited to, one or more of palladium chloride, palladium nitrate, palladium acetate, sodium tetrachloropalladate, palladium tetra ammine dichloride, palladium trifluoroacetate, palladium diacetylacetonate, or palladium hexafluoroacetylacetonate, with palladium chloride being preferred.
In the above preparation method, step d) is a catalyst treatment step. The impregnated solid is dried and then calcined in air. The calcination temperature is preferably 400 to 650 ℃. The volume ratio of gas to agent is 500-1200:1, and the roasting time is preferably 2-8 hours. The roasted catalyst needs to be reduced, the reduction is carried out in a hydrogen atmosphere, the proper reduction temperature is 450-550 ℃, the volume ratio of gas to agent is 400-1200:1, and the reduction time is 2-6 hours.
According to a preferred embodiment of the invention, the catalyst of the invention has a pore volume of 0.4 to 1.0mL/g and a specific surface area of 80 to 300m 2 /g。
According to a preferred embodiment of the invention, in the catalyst of the invention, the proportion of pores with a pore radius volume distribution of less than 3nm, 3 to 5nm, 5 to 10nm and greater than 10nm is less than 1%, 2 to 10%, 10 to 20% and 70 to 90%, respectively. In the pore radius volume distribution of the catalyst of the invention, the proportion of pores with larger pore radius (pores with the diameters of 5-10 nm and more than 10 nm) is higher. In particular, pores greater than 10nm are the predominant pores in the catalysts of the present invention. While not wishing to be bound by theory, such larger pore based catalysts facilitate liquid phase reaction mass and heat transfer and prevent the plugging of catalyst channels by trace amounts of gum contained in the oil.
The catalyst of the present invention does not need to be presulfided before use. Whereas conventional catalyst presulfiding is a treatment of the catalyst by adding sulfur-containing compounds to hydrogen, the sulfur content in the hydrogen is 0.01 to 1.0%, preferably 0.04 to 1.0% (relative to the mass of the catalyst). The presulfiding temperature is preferably 370-450 ℃.
The catalyst of the invention is suitable for hydrofining reaction of the reformed oil, and comprises the contact reaction of the reformed oil with the catalyst of the invention under the condition of liquid phase hydrogenation. The liquid phase hydrogenation reaction conditions are as follows: the pressure is 0.5-5.0 MPa, preferably 1.0-3.0 MPa, the temperature is 50-300 ℃, preferably 80-170 ℃, the hydrogen-oil volume ratio is 2-100, preferably 2-10, and the feeding volume airspeed is 0.50-30.0 h -1 Preferably 4.0 to 20.0h -1 . According to the hydrofining reaction of the reformed oil, the olefin removal rate is more than 98%, the bromine index of the product is less than 20mg Br/100g oil, and the aromatic hydrocarbon loss is less than 0.1wt%. The catalyst of the invention is adopted to carry out liquid phase reaction, and the subsequent reaction products do not need to be subjected to clay treatment, so that the olefin removal process of completely replacing clay can be realized.
According to an exemplary embodiment of the present invention, reformate suitable for the present invention includes reformate benzene fraction, reformate BTX fraction, full fraction reformate or reformate raffinate.
The invention is further illustrated by the following examples, but is not limited thereto.
Example 1
Preparation of sulfate-containing Al of the invention 2 O 3 Carrier body
Pseudo-boehmite powder produced by the Kaolin catalyst Co., ltd.) by adopting a sodium metaaluminate and aluminum sulfate precipitation method is prepared according to the following powder: sesbania powder: nitric acid: acetic acid: citric acid: the water=50:1:2:3:3:40 mass ratio is kneaded uniformly, then extruded, dried for 12 hours at 120 ℃ and baked for 4 hours at 450 ℃. The carrier is treated for 3 hours at 800 ℃ by controlling the air-to-carrier gas-to-gas ratio of 700:1 and introducing saturated water vapor at 120 ℃ to prepare Al 2 O 3 Carrier ZT-1, in which SO 4 2- The ion content was 0.69 mass% of the dry alumina. The physicochemical properties of the carrier are shown in Table 1.
Example 2
Preparation of sulfate-containing Al of the invention 2 O 3 A carrier.
As in example 1, al was produced with the exception that the temperature of the hydrothermal treatment of the support was 950 ℃ 2 O 3 The physicochemical properties of the carrier ZT-2 are shown in Table 1.
Comparative example 1
Preparation of conventional gamma-Al 2 O 3 A carrier.
Pseudo-boehmite powder (manufactured by Sasol company, germany) synthesized by adopting an aluminum alkoxide hydrolysis method is prepared according to the following steps: methylcellulose: nitric acid: acetic acid: citric acid: uniformly kneading the materials according to the mass ratio of water=50:1:2:3:3:40, extruding the materials, drying the wet materials at 120 ℃ for 12 hours, and roasting at 650 ℃ for 4 hours to obtain gamma-Al 2 O 3 The physical and chemical properties of the carrier DBZT-1 are shown in Table 1, wherein sulfate radical is derived from trace sulfur and analysis errors in raw materials used for preparation.
Comparative example 2
The procedure of comparative example 1 was followed except that DBZT-1 was hydrothermally modified by the procedure of example 1 to give DBZT-2 as a support having physicochemical properties as shown in Table 1, in which sulfate radicals were derived from trace amounts of sulfur and analytical errors in the raw materials used in the preparation.
Example 3
The catalyst of the present invention was prepared.
50 g of ZT-1 carrier prepared in example 1 was taken, nickel nitrate, palladium chloride and hydrochloric acid were prepared into impregnation solutions, and the impregnation solutions were respectively made to contain Ni 5.0wt%, pd 0.20wt% and Cl 1.8wt% (relative to the mass of dry alumina), and the liquid/solid volume ratio was 1.5. The carrier and the impregnating solution were poured into a 500 ml flask, and the mixture was impregnated with the impregnating solution on a rotary vacuum evaporator (manufactured by Shanghai Asia Biochemical apparatus Co., ltd.) at 30℃and 0.008MPa at a rotation speed of 0.03 m/s for 3 hours, and the solid was dried at 120℃for 12 hours by vacuum-pumping at 70 ℃. Activating in dry air at 500 deg.C with gas/agent volume ratio of 700 for 4 hr, and then using H at 480 deg.C with gas/agent volume ratio of 500 2 Reduction for 4 hours gave catalyst Cat-1, whose composition is shown in Table 2.
Comparative example 3
A catalyst was prepared as in example 3, except that the support was DBZT-1, resulting in catalyst DBCat-1 having the composition shown in Table 2.
Comparative example 4
A catalyst was prepared as in example 3, except that after reduction of the catalyst, 0.12wt% (relative to the mass of the catalyst) of hydrogen sulfide was added to a hydrogen stream at 425℃to presulfide the catalyst, giving a catalyst DBCat-2 having the composition shown in Table 2.
Example 4
The catalyst of the present invention was prepared.
A catalyst was prepared as in example 3, except that 7.85wt% of Ni, 0.15wt% of Pd and 1.8wt% of Cl (relative to the mass of dry alumina) were contained in the impregnation liquid, and Cat-2 was prepared, the composition of which is shown in Table 2.
Example 5
The catalyst of the present invention was prepared.
A catalyst was prepared according to example 3, the different supports being ZT-2, the impregnation also containing Pt 0.1wt% and the catalyst being Cat-3, the composition of which is shown in Table 2.
Comparative example 5
Comparative catalyst DBCat-3 was prepared as in example 1 of comparative patent CN1448474A and its composition is shown in Table 2.
Example 6
The catalyst of the present invention was prepared.
A catalyst was prepared as in example 3, except that the impregnation liquid was made to contain Ni 5wt%, pd 0.20wt%, pt 0.10wt% and Cl 1.8wt% (relative to the mass of dry alumina), to prepare a catalyst Cat-4, the composition of which is shown in Table 2.
Comparative example 6
Comparative catalyst DBCat-4 was prepared according to comparative patent CN104014337A, example 4, with the composition shown in Table 2.
Comparative example 7
A catalyst was prepared as in example 3, except that the impregnation liquid contained Pd 0.20wt%, pt 0.10wt%, cl 1.8wt% (relative to the mass of dry alumina) and no Ni, to prepare a catalyst DBCat-5, the composition of which is shown in Table 2.
Example 7
10mL of the catalyst was charged into a medium-sized high-pressure micro-reaction evaluation device manufactured by Shanghai Michel laboratory equipment, inc., and the reaction performance of the catalyst was evaluated using the full-cut reformate having the properties shown in Table 3 as a raw material. The evaluation conditions were: the reaction temperature is 80 ℃, the pressure is 2.0MPa, and the feeding weight airspeed is 12h -1 The hydrogen/oil volume ratio was 10:1 and the results of each catalyst reaction are shown in Table 4.
TABLE 1 physicochemical Properties of the Carrier
TABLE 2 catalyst composition
TABLE 3 Properties of full fraction reformate feedstock
TABLE 4 reactivity of catalysts
As can be seen from tables 2 and 4, the catalyst of the present invention has an extremely high olefin removal rate and an extremely low aromatic hydrocarbon loss, compared with the comparative catalyst, indicating that the catalyst has high activity, good stability and high selectivity.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "inner", "outer", "front", "rear", "left", "right", etc. are directions or positional relationships based on the operation state of the present invention are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements to be referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
The invention has been described above in connection with preferred embodiments, which are, however, exemplary only and for illustrative purposes. On this basis, the invention can be subjected to various substitutions and improvements, and all fall within the protection scope of the invention.
Claims (10)
1. The catalyst for removing olefin from reformed oil includes alumina carrier containing sulfate radical, main active component of nickel, assistant and optional halogen, and the assistant is at least one Pd-containing VIII metal.
2. The catalyst of claim 1 wherein the promoter is palladium or a combination of palladium and platinum.
3. Catalyst according to claim 1 or 2, characterized in that the catalyst comprises a sulphate-containing alumina support, a main active component nickel, an auxiliary agent of a metal of group viii containing at least palladium and halogen, the main active component nickel content of the catalyst being 3-20 wt%, preferably 5-15 wt%, the auxiliary agent content being 0.05-0.5 wt%, preferably 0.1-0.3 wt%, the halogen content being 0.2-3 wt%, preferably 0.6-2 wt%, the elemental sulphur content being 0.03-1 wt%, preferably 0.1-0.5 wt%, based on the weight of the support.
4. A catalyst according to any one of claims 1 to 3, wherein the catalyst has a pore volume of 0.4 to 1.0mL/g and a specific surface area of 80 to 300m 2 /g。
5. The catalyst of any of claims 1 to 4, wherein the proportion of pores in the catalyst in the volume distribution of pore radius is less than 1%, 2 to 10%, 10 to 20% and 70 to 90%, respectively, of pores in the range of 3nm, 3 to 5nm, 5 to 10nm and greater than 10 nm.
6. The catalyst of any one of claims 1 to 5, wherein the preparation of the catalyst comprises the steps of:
a) The aluminum hydroxide powder used for preparing the alumina carrier containing sulfate radical is prepared by the reaction of sodium metaaluminate and aluminum sulfate precipitation method;
b) Roasting aluminum hydroxide powder at 400-1000 ℃ after forming, and then treating the aluminum hydroxide powder for 0.5-12 hours at 300-1000 ℃ by using saturated/supersaturated water vapor at 100-150 ℃ to obtain an alumina carrier containing sulfate radicals, wherein the amount of water vapor passing through the carrier is 0.2-10 times of the weight of the carrier;
c) Contacting the support obtained in b) with an aqueous precursor solution comprising halogen and a group viii metal comprising at least nickel and/or palladium to obtain a catalyst precursor;
d) Drying the catalyst precursor obtained in c) at 60-200 ℃ for 6-12 hours, activating for 2-6 hours at 400-650 ℃ in air atmosphere, and finally reducing for 2-6 hours at 450-550 ℃ in hydrogen atmosphere.
7. The catalyst of claim 6 wherein the precursor of the group viii metal containing at least nickel is selected from one or more of nickel chloride, nickel nitrate, nickel acetate, nickel carbonate, nickel sulfate, nickel hydroxide, nickel formate, nickel acetate, nickel nitrite.
8. The catalyst of claim 6 wherein the precursor of the group viii metal containing at least palladium is selected from one or more of palladium chloride, palladium nitrate, palladium acetate, sodium tetrachloropalladate, dichlorotetraammine palladium, palladium trifluoroacetate, palladium diacetylacetonate, or palladium hexafluoroacetylacetonate.
9. A hydrofining method of reformate includes the steps of heating reformate at 50-300 deg.C, 0.5-5.0 MPa and 0.5-30.0 h weight airspeed -1 The catalyst of any one of claims 1-9 is contacted and reacted under the liquid phase hydrogenation condition that the volume ratio of hydrogen to oil is 2-100, the bromine index of the product is less than 20mgBr/100g of oil, and the aromatic hydrocarbon loss is less than 0.1w percent.
10. The method of claim 9, wherein the reformate is selected from one or more of a reformate benzene fraction, a reformate BTX blend fraction, a full fraction reformate, and a reformate raffinate.
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