CN107486201A - It is a kind of for the catalyst of selective hydrogenation of cracked gasoline and its preparation and application - Google Patents
It is a kind of for the catalyst of selective hydrogenation of cracked gasoline and its preparation and application Download PDFInfo
- Publication number
- CN107486201A CN107486201A CN201610408191.4A CN201610408191A CN107486201A CN 107486201 A CN107486201 A CN 107486201A CN 201610408191 A CN201610408191 A CN 201610408191A CN 107486201 A CN107486201 A CN 107486201A
- Authority
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- China
- Prior art keywords
- catalyst
- palladium
- carrier
- solution
- drippolene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 165
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 21
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 17
- 229920001249 ethyl cellulose Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- -1 Titanium oxide-aluminum oxide compound Chemical class 0.000 claims description 11
- 239000001856 Ethyl cellulose Substances 0.000 claims description 10
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- PHTHEUNUXVDUOD-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[O-2].[Al+3] PHTHEUNUXVDUOD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 125000001246 bromo group Chemical class Br* 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004517 catalytic hydrocracking Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- 238000003756 stirring Methods 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000007598 dipping method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 238000000643 oven drying Methods 0.000 description 8
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DCRIQAAPAFMPKP-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical class [O-2].[O-2].[Al+3].[Ti+4] DCRIQAAPAFMPKP-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920013819 hydroxyethyl ethylcellulose Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004448 titration Methods 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/06—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 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
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of catalyst for selective hydrogenation of cracked gasoline, it includes titanium oxide alumina composite carrier, and the Metal Palladium on the complex carrier is supported on, wherein the content of Metal Palladium is calculated as 0.2 0.4wt%, preferably 0.25 0.35wt% based on the total catalyst weight.Application the invention further relates to the preparation method of the catalyst and its in hydrocracking gasoline is selected.Catalyst provided by the invention has good catalytic activity and stability, and has stronger anti-impurity ability and longer service life, can carry out selective hydrogenation reaction at low temperature.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of catalyst and its preparation for selective hydrogenation of cracked gasoline
Methods and applications.
Background technology
Drippolene C5-C9Cut is the accessory substance of ethylene industry.According to the difference of cracking stock and cracking severity, it is produced
Amount accounts for more than the 50 weight % of ethylene production capacity, and wherein arene content accounts for 40-80 weight %, therefore drippolene C5-C9Evaporate
Point it is the main source of aromatic hydrocarbons.C is cut in industrial production8And C9Cut, through one-stage hydrogenation, remove height unsaturated hydrocarbons, such as chain
Conjugated diene, styrene, alkynes and cyclic conjugated diene class, then through Secondary hydrodesulfurization, removing monoene and sulphur, nitrogen, oxygen etc. has
After machine compound, C8Cut is used to produce dimethylbenzene, and C9Cut is used to produce aromatic solvent naphtha.C8Cut also can be only through once
Hydrogenation, diolefin is removed, retains most of monoene, the motor petrol adulterant or octane number stablized are higher (to be greater than
70) motor petrol.
At present, industrial drippolene C5-C9Fraction selective hydrogenation is mainly Ni/Al with catalyst2O3Or Pd/Al2O3,
There is Pd-Cr/Al2O3Bimetallic catalyst.Due to drippolene C8And C9In heavy distillat the impurity such as As, S, O, N and gum level compared with
Height, catalyst is inactivated quickly, thus must not infrequently activate and regenerated catalyst.The industrial Pd/Al used now2O3Urge
It is 7 days that the regeneration period of agent is most short.
Chinese patent application CN1361231A discloses a kind of selective hydrogenation catalyst for diolefin, and its carrier is to adopt
The aluminium titanium composite oxide prepared with chemical coprecipitation, the wherein weight percent content of aluminum oxide are 1-99%, carrier hole
Footpath, which is distributed at 50nm and 1000nm, there is bimodal, load Pd active components and optional IB and/or IA or Group IIA metal,
The advantages that active high, selectivity is high, sulfur resistive and arsenic ability are strong, but its low temperature active still has much room for improvement.
United States Patent (USP) US6,576,586 discloses a kind of selective hydrogenation of cracked gasoline catalysis that can be run under high-speed
Agent, wherein active component Pd load capacity are the 0.05-0.4% of catalyst weight, using alkali metal or/and alkaline-earth metal to help
Agent, its load capacity are the 0.05-2.0% of catalyst weight, and carrier is the Al that phase is mixed with δ phases and α2O3, wherein α phases
Al2O30.5-5wt% is accounted for, the pore volume of carrier is 0.5-0.9ml/g, and aperture is distributed in 4-20nm, specific surface area 70- mostly
140m2/g.However, the low temperature active of the catalyst and selectivity have much room for improvement.
It is badly in need of in current industrial with active compared with high/low temperature, higher anti-impurity poisoning capability and the appropriate selection for holding glue ability
Hydrogenation catalyst, to increase the regeneration period of catalyst, so as to extend the service life of catalyst.
The content of the invention
To solve the problems, such as that prior art is present, the present inventor is carried out to pyrolysis gasoline selective hydrogenation catalyst
Research extensively and profoundly, as a result find by using complex carrier titanium dioxide-aluminum oxide, and from Metal Palladium as activearm
Point, the concerted catalysis effect of carrier and active component is improved, has obtained a kind of there is more preferable low temperature active, selectivity and surely
Qualitatively selective hydrogenation catalyst.
On the one hand, the invention provides a kind of catalyst for selective hydrogenation of cracked gasoline, it includes titanium oxide-oxidation
It is total that aluminium complex carrier, and the Metal Palladium being supported on the complex carrier, the wherein content of Metal Palladium are based on the catalyst
Weight is calculated as 0.2-0.4wt%, preferably 0.25-0.35wt%.
According to the present invention, in the complex carrier, the content of titanium oxide is preferably 10- based on alumina weight meter
20wt%, more preferably 13-17wt%.
In the present invention, the specific surface area of the catalyst is preferably 80-180m2/ g, more preferably 120-150m2/g.It is described
The pore volume of catalyst is preferably 0.4-1.3ml/g, more preferably 0.5-1.0ml/g.Most probable pore size is preferably 9-15nm, more preferably
11-14nm。
On the other hand, the invention provides a kind of preparation method of the catalyst, comprise the following steps：
I) by H2O2Solution spraying is immersed in inorganic acid solution in Titanium oxide-aluminum oxide compound after primary drying,
It is scrubbed again, redrying, obtain carrier；
II) palladium source and additive are dissolved in the solution that the element containing palladium is made in organic solvent, by the carrier impregnation in institute
In the solution for stating the element containing palladium, then through drying, roasting, obtain catalyst prod.
In the present invention, according to step I) hydroxy radical content on complex carrier surface can be effectively improved, be advantageous to Metal Palladium
It is preferably scattered in carrier surface.
According to the present invention, in step I) in, oxidation commonly used in the art can be selected in the Titanium oxide-aluminum oxide compound
Titanium-alumina compound, the titanium oxide-oxidation being preferably prepared by method disclosed in Chinese patent application 02146005.1
Aluminium compound.
In step I) in, the H2O2The concentration of solution is preferably 10-30wt%, more preferably 20-25wt%.It is described once
Dry temperature is preferably 60-120 DEG C, and the time of primary drying is preferably 12-24h.
The inorganic acid preferably includes at least one of nitric acid, hydrochloric acid and phosphoric acid.The concentration of the inorganic acid solution is excellent
Elect 0.01-5mol/L, more preferably 0.2-2mol/L as.The temperature of the redrying is preferably 100-120 DEG C, redrying
Time is preferably 12-24h.The present invention is by step I) carrier surface is modified, improve carrier surface hydroxyl base
The content of group, the polarity of carrier surface is enhanced, the scattered of activity component metal palladium can be promoted.
According to the present invention, in step II) in, the organic solvent preferably includes at least one of benzene, toluene or acetone.
The volume ratio of the carrier and organic solvent is preferably 1:(1-3).
The palladium source preferably includes at least one of nitrate of palladium acetylacetonate, the halide of palladium and palladium, preferably palladium
Halide.Weight meter of the content of palladium element based on the carrier is preferably 0.01-0.4wt% in the palladium source, more preferably
0.25-0.35wt%.
In step II) in, the additive preferably includes hydroxyethyl cellulose, ethyl cellulose and acetylbutyrylcellulose
At least one of.The mol ratio of palladium element is preferably (0.01-2) in additive and the palladium source:1, more preferably (0.1-1):
1。
In the present invention, the chemical formula of the hydroxyethyl cellulose is (C2H6O2)x, wherein x is preferably 1.4-2.0.It is described
The chemical formula of ethyl cellulose is [C6H7O2(OC2H5)3]n, wherein n is preferably 20-50.The chemistry of the acetylbutyrylcellulose
Formula is (C4H8O2)a(C2H4O2)b, wherein a is preferably 13-16, and b is preferably 26-47.
In step II) in, the time preferred 12-24h of the dipping, 1h is preferably first stirred at room temperature and enters Mobile state leaching
Stain, then stand and carry out static dipping.It is preferred that the solution of the element containing palladium is evaporated before it is dried, it is described to be evaporated preferably in 100-
Carried out in 120 DEG C of oil bath.Preferred 80-120 DEG C of the temperature of the drying, preferred 1-4h of dry time.The temperature of the roasting
Preferred 280-320 DEG C is spent, the time preferred 1-4h of roasting.
The present invention is by improving vehicle treated method and method for preparing catalyst, in the association of carrier surface modification and additive
Under same-action, Metal Palladium can be made dispersedly more preferable in carrier surface.
Present invention also offers a kind of method for carrying out selecting hydrogenation to drippolene, comprise the following steps：
The catalyst is reduced；
Hydrogenated pyrolysis gasoline is carried out using the catalyst；
Preferably, the drippolene is drippolene C5-C9Cut, more preferably C8And C9Heavy distillat.
The reduction of the catalyst uses catalyst reduction method commonly used in the art.In accordance with the present invention it is preferred that
The temperature of the reduction is preferably 100-150 DEG C, and Hydrogen Vapor Pressure is preferably normal pressure, and hydrogen flowing quantity is preferably that 2-15ml/min.g is urged
Agent, and time are preferably 3-4 hours.
According to the present invention, the temperature of the hydrogenated pyrolysis gasoline is preferably 50-60 DEG C, and pressure is preferably 2.6-3.0MPa,
Hydrogen to oil volume ratio is preferably (50-80):1, and liquid hourly space velocity (LHSV) is preferably 8-12h-1.This is used in selective hydrogenation of cracked gasoline
The catalyst provided is provided, reaction can be made to carry out at low temperature.
In the present invention, term " liquid hourly space velocity (LHSV) " refers to the liquid phase reactor thing of per volume of catalyst processing per hour
Volume.Term " low temperature " refers to the temperature that hydrogenated pyrolysis gasoline reaction (such as more than 100 DEG C) is relatively low compared with prior art
Degree.
According to the present invention, the drippolene is preferably drippolene C5-C9Cut, more preferably C8And C9Heavy distillat.At this
In invention, the drippolene is preferably diene value 20-40g iodine/100g oil, and the cracking vapour of bromine valency 40-70g bromines/100g oil
Oily raw material.
Catalyst provided by the invention has advantage and effect following prominent：In drippolene C5-C9Cut, especially C8
And C9In the selective hydrogenation reaction of heavy distillat, catalyst provided by the invention has very high low temperature hydrogenation activity and selectivity,
Long reaction is activity stabilized, service life length, and has higher anti-impurity poisoning capability and hold glue ability.
Embodiment
The present invention will be more fully described by the following example the present invention, can make those skilled in the art that this hair be more fully understood
It is bright, but these embodiments do not form any restrictions to the scope of the present invention.
Product bromine valency：Determined by volumetric analysis (SH/T0236-92).For weighing unsaturated hydrocarbons in gasoline sample
Content, the grams of the bromine consumed with 100g gasoline samples represent.
Product diene value：Determined by professional standard UOP326.For weighing the content of alkadienes in gasoline sample, with
The grams of the iodine that 100g gasoline samples are consumed represents.
Titanium oxide-aluminum oxide compound：It is prepared according to the method that patent application 02146005.1 is related to.
Metal palladium content in catalyst prod：Using spectrophotometry.
Embodiment 1
Use 20wt%H2O2Solution spraying fully soaks in 100g Titanium oxide-aluminum oxide compound to surface, in 60 DEG C of bakings
It is dry.The compound of drying is immersed in 24h in 0.4mol/L dilute nitric acid solution (concentration 2.5wt%), during which stir three to
, obtained compound is put into standby after 110 DEG C of oven for drying 12h for five times, then carrier is washed with deionized to pH=7, obtained
To titanium dioxide-aluminum oxide carrier.
By 2g palladium acetylacetonates and 15.6g ethyl celluloses (chemical formula [C6H7O2(OC2H5)3]24) be dissolved in 200mL toluene
The toluene solution of the element containing palladium is made, the mol ratio of wherein ethyl cellulose and palladium in palladium acetylacetonate is 0.4:1.Will be above-mentioned
Obtained carrier impregnation after stirring dipping 1h, is sufficiently impregnated 12h at room temperature in the toluene solution of the element containing palladium.
After stirring is evaporated solution in 110 DEG C of oil baths, carrier is taken out in 100 DEG C of oven drying 2h, then 2h is calcined at 300 DEG C, palladium is made
Base catalyst A.
After testing, the content of Metal Palladium is 0.3wt% in palladium-based catalyst A.
Embodiment 2
Use 20wt%H2O2Solution spraying fully soaks in 100g Titanium oxide-aluminum oxide compound to surface, 60 DEG C of bakings
It is dry, the compound of drying is immersed in 24h in 0.4mol/L dilute nitric acid solution (concentration 2.5wt%), during which stir three to
, obtained compound is put into standby after 110 DEG C of oven for drying 12h for five times, then be washed with deionized to pH=7, obtains oxygen
Change titanium-alumina support.
By 1.2g palladium bichlorides and 16.2g ethyl celluloses (chemical formula [C6H7O2(OC2H5)3]24) be dissolved in 200mL toluene and making
Into the toluene solution of the element containing palladium, the mol ratio of wherein ethyl cellulose and palladium in palladium bichloride is 0.4:1.By load obtained above
Body is immersed in the toluene solution of the element containing palladium, after stirring dipping 1h, is sufficiently impregnated 12h at room temperature.In 110 DEG C of oil baths
After middle stirring is evaporated solution, carrier is taken out in 100 DEG C of oven drying 2h, then 2h is calcined at 300 DEG C, palladium-based catalyst B is made.
After testing, the content of Metal Palladium is 0.2wt% in palladium-based catalyst B.
Embodiment 3
Use 20wt%H2O2Solution spraying fully soaks in 100g Titanium oxide-aluminum oxide compound to surface, 60 DEG C of bakings
It is dry, the compound of drying is immersed in 24h in 0.4mol/L dilute nitric acid solution (concentration 2.5wt%), during which stir three to
, obtained compound is put into standby after 110 DEG C of oven for drying 24h for five times, then be washed with deionized to pH=7, obtains oxygen
Change titanium-alumina support.
By 3.8g palladium acetylacetonates and 15.6g acetylbutyrylcelluloses (chemical formula (C4H8O2)15(C2H4O2)30) be dissolved in
The mol ratio of the toluene solution of the element containing palladium, wherein acetylbutyrylcellulose and palladium in palladium acetylacetonate is made in 200mL toluene
For 0.4:1.By carrier impregnation obtained above in the toluene solution of the element containing palladium, after stirring dipping 1h, at room temperature
It is sufficiently impregnated 12h.After stirring is evaporated solution in 110 DEG C of oil baths, carrier is taken out in 100 DEG C of oven drying 2h, then at 300 DEG C
2h is calcined, palladium-based catalyst C is made.
After testing, the content of Metal Palladium is 0.4wt% in palladium-based catalyst C.
Embodiment 4
Use 30wt%H2O2Solution spraying fully soaks in 100g Titanium oxide-aluminum oxide compound to surface, in 60 DEG C of bakings
It is dry, the compound of drying is immersed in 24h in 1mol/L dilute nitric acid solution (concentration 6.1wt%), during which stirs three to five
It is secondary, then be washed with deionized to pH=7, obtained compound is put into standby after 110 DEG C of oven for drying 24h, aoxidized
Titanium-alumina support.
By 2g palladium acetylacetonates and 15.6g ethyl celluloses (chemical formula [C6H7O2(OC2H5)3]24) be dissolved in 200mL toluene
The toluene solution of the element containing palladium is made, the mol ratio of wherein ethyl cellulose and palladium in palladium acetylacetonate is 0.4:1.By above-mentioned system
The carrier impregnation obtained after stirring dipping 1h, is sufficiently impregnated 12h at room temperature in the toluene solution of the element containing palladium.110
After stirring is evaporated solution in DEG C oil bath, carrier is taken out in 100 DEG C of oven drying 2h, then 2h are calcined at 300 DEG C, obtained palladium base is urged
Agent D.
After testing, the content of Metal Palladium is 0.3wt% in palladium-based catalyst D.
Embodiment 5
Use 30wt%H2O2Solution spraying fully soaks in 100g Titanium oxide-aluminum oxide compound to surface, 60 DEG C of bakings
It is dry, the compound of drying is immersed in 24h in 4mol/L dilute nitric acid solution (concentration 21.5wt%), during which stirs three to five
It is secondary, then be washed with deionized to pH=7, obtained compound is put into standby after 110 DEG C of oven for drying 24h, aoxidized
Titanium-alumina support.
By 2g palladium acetylacetonates and 15.6g ethyl celluloses (chemical formula [C6H7O2(OC2H5)3]24) be dissolved in 200mL toluene
The toluene solution of the element containing palladium is made, the mol ratio of wherein ethyl cellulose and palladium in palladium acetylacetonate is 0.4:1.By above-mentioned system
The carrier impregnation obtained after stirring dipping 1h, is sufficiently impregnated 12h at room temperature in the toluene solution of the element containing palladium.110
After stirring is evaporated solution in DEG C oil bath, carrier is taken out in 100 DEG C of oven drying 2h, then 2h are calcined at 300 DEG C, obtained palladium base is urged
Agent E.
After testing, the content of Metal Palladium is 0.3wt% in palladium-based catalyst E.
Embodiment 6
Use 10wt%H2O2Solution spraying fully soaks in 100g Titanium oxide-aluminum oxide compound to carrier surface, 60
DEG C drying, the compound of drying is immersed in 24h in 0.15mol/L dilute nitric acid solution (concentration 1.0wt%), during which stir
, obtained compound is put into standby after 110 DEG C of oven for drying 24h for three to five times, then be washed with deionized to pH=7, obtained
To titanium dioxide-aluminum oxide carrier.
By 2g palladium acetylacetonates and 15.6g ethyl celluloses (chemical formula [C6H7O2(OC2H5)3]24) be dissolved in 200mL toluene
The toluene solution of the element containing palladium is made, the mol ratio of wherein ethyl cellulose and palladium in palladium acetylacetonate is 0.4:1.Will be above-mentioned
Obtained carrier impregnation after stirring dipping 1h, is sufficiently impregnated 12h at room temperature in the toluene solution of the element containing palladium.
After stirring is evaporated solution in 110 DEG C of oil baths, carrier is taken out in 100 DEG C of oven drying 2h, then 2h is calcined at 300 DEG C, palladium is made
Base catalyst F.
After testing, the content of Metal Palladium is 0.3wt% in palladium-based catalyst F.
Comparative example 1
By 2g palladium acetylacetonates and 15.6g ethyl celluloses (chemical formula [C6H7O2(OC2H5)3]24) be dissolved in 200mL toluene
The toluene solution of the element containing palladium is made, the mol ratio of wherein ethyl cellulose and palladium in palladium acetylacetonate is 0.4:1.By 100g oxygen
Change titanium-alumina compound to be immersed in the toluene solution of the element containing palladium, the volume ratio of the compound and solution is 1:
2.After stirring dipping 1h, 12h is sufficiently impregnated at room temperature.In 110 DEG C of oil baths stirring be evaporated solution after, by compound take out in
100 DEG C of oven drying 2h, then 2h is calcined at 300 DEG C, palladium-based catalyst a is made.
After testing, the content of Metal Palladium is 0.3wt% in palladium-based catalyst a.
Comparative example 2
100g Titanium oxide-aluminum oxide compounds are immersed in 1mol/L dilute nitric acid solution (concentration 6.1wt%)
24h, during which stir three to five times, then be washed with deionized to pH=7, obtained compound is put into 110 DEG C of oven for drying
It is standby after 24h.Standby compound is immersed in 30wt%H2O224h in solution, during which stir three to five times, then use deionization
Water washing obtains standby carrier to pH=7 after placing into 110 DEG C of oven for drying 24h.
By 2g palladium acetylacetonates and 15.6g ethyl celluloses (chemical formula [C6H7O2(OC2H5)3]24) be dissolved in 200mL toluene
The toluene solution of the element containing palladium is made, the mol ratio of wherein ethyl cellulose and palladium in palladium acetylacetonate is 0.4:1.By above-mentioned system
The carrier impregnation obtained is in the toluene solution of the element containing palladium.After stirring dipping 1h, 12h is sufficiently impregnated at room temperature.110
After stirring is evaporated solution in DEG C oil bath, carrier is taken out in 100 DEG C of oven drying 2h, then 2h are calcined at 300 DEG C, obtained palladium base is urged
Agent b.
After testing, the content of Metal Palladium is 0.3wt% in palladium-based catalyst b.
Embodiment 7
Selective hydrogenation of cracked gasoline reacts：
Carried out on 100ml small fixeds hydrogenation evaluating apparatus.The reactor of the evaluating apparatus is long 1.2m, interior
Footpath 26mm reaction tube, loaded catalyst 100ml.The process conditions such as reaction temperature, pressure are by microcomputer automatic control.
Catalyst A made from 100ml embodiments 1 is loaded into the reaction tube of hydrogenation evaluating apparatus, is in Hydrogen Vapor Pressure
2.8MPa, temperature are 110 DEG C and hydrogen flowing quantity is to reduce 8 hours under conditions of 4ml/min.g catalyst.Then in reaction temperature
50 DEG C, Hydrogen Vapor Pressure 2.8Mpa, hydrogen to oil volume ratio 80:1st, fresh feed liquid hourly space velocity (LHSV) is 3h-1It is with total liquid hourly space velocity (LHSV)
12h-1Under conditions of be passed through drippolene C8(diene value of the cut is 20.27g iodine/100g oil, bromine valency 40.36g to cut
Bromine/100g oil, gum level are 232mg/100ml oil, nitrogen content is 3.4mg/100ml oil, oxide content 2.19g/
100ml oil, sulfur content is 110ppm and arsenic content is 180ppb).Hydrogenation reaction the results are shown in Table 1.
Embodiment 8-12
The catalyst B-F that embodiment 8-12 respectively obtains embodiment 2-6 carries out selective hydrogenation of cracked gasoline reaction, reaction
Condition is the same as embodiment 7.Obtained result of the test is listed in Table 1 below.
Comparative example 3-4
Selective hydrogenation of cracked gasoline reacts：The catalyst a and b that comparative example 1 and 2 is obtained carry out selective hydrogenation of cracked gasoline
Reaction, reaction condition is the same as embodiment 7.Obtained result of the test is listed in Table 1 below.
Table 1
Embodiment 13
Catalyst D made from 100ml embodiments 4 is packed into 100ml small fixeds hydrogenation evaluating apparatus and split
Change gasoline selective hydrogenation reaction.Reaction condition and the difference of embodiment 7 are that fresh feed liquid hourly space velocity (LHSV) is 2.0h-1, it is total
Charging liquid hourly space velocity (LHSV) is 8.0h-1And the reaction time is 1000 hours.Hydrogenation reaction the results are shown in Table 2.
Table 2
Understand that catalyst provided by the invention has good catalytic activity and stability, stronger with reference to table 1-2 result
Anti- impurity and hold glue ability (colloid in such as anti-gasoline stocks, nitrogen, oxide, the ability of sulphur and arsenic) and longer use longevity
Life.Further, catalyst provided by the invention (such as 50-60 DEG C) can carry out selective hydrogenation reaction, explanation at low temperature
Catalyst has preferable cryogenic property.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that each side of the invention recorded, different embodiments
Each several part and the various features enumerated can be combined or all or part of exchange.In above-mentioned each embodiment, that
A little embodiments with reference to another embodiment can be combined suitably with other embodiment, and this is by by this area skill
Art personnel are to understand.In addition, it will be understood to those of skill in the art that description above is only the mode of example, not purport
In the limitation present invention.
Claims (10)
1. a kind of catalyst for selective hydrogenation of cracked gasoline, it includes titanium dioxide-aluminum oxide composite carrier, and is supported on
The content of Metal Palladium on the complex carrier, wherein Metal Palladium is calculated as 0.2-0.4wt% based on the total catalyst weight, excellent
Select 0.25-0.35wt%.
2. catalyst according to claim 1, it is characterised in that the content of the titanium oxide is calculated as based on alumina weight
10-20wt%, preferably 13-17wt%.
3. a kind of preparation method of catalyst as claimed in claim 1 or 2, comprises the following steps：
I) by H2O2Solution spraying is immersed in inorganic acid solution in Titanium oxide-aluminum oxide compound after primary drying, then is passed through
Washing, redrying, obtains carrier；
II) palladium source and additive are dissolved in the solution that the element containing palladium is made in organic solvent, the carrier impregnation is contained described
In the solution of palladium element, then through drying, roasting, obtain catalyst prod.
In 4. according to the method for claim 3, it is characterised in that in step I), the H2O2The concentration of solution is 10-
30wt%, preferably 20-25wt%；And/or
The concentration of the inorganic acid solution is 0.01-5mol/L, preferably 0.2-2mol/L.
5. the method according to claim 3 or 4, it is characterised in that in step II) in, the additive includes ethoxy
At least one of cellulose, ethyl cellulose and acetylbutyrylcellulose；
The mol ratio of palladium element is (0.01-2) in additive and the palladium source:1, preferably (0.1-1):1；And/or
Weight of the content of palladium element based on the carrier is calculated as 0.01-0.4wt% in the palladium source.
6. according to the method described in any one in claim 3-5, it is characterised in that in step II) in, the temperature of the roasting
Spend for 280-320 DEG C, the time of roasting is 1-4h.
7. a kind of method for carrying out selecting hydrogenation to drippolene, comprises the following steps：
Catalyst prepared by the catalyst of claim 1 or 2 or the method as any one of claim 3-6 is gone back
It is former；
Hydrogenated pyrolysis gasoline is carried out using the catalyst；
Preferably, the drippolene is drippolene C5-C9Cut, more preferably C8And C9Heavy distillat.
8. according to the method for claim 7, it is characterised in that the temperature of the hydrogenated pyrolysis gasoline is 50-60 DEG C, pressure
For 2.6-3.0MPa, hydrogen to oil volume ratio is (50-80):1, and liquid hourly space velocity (LHSV) is 8-12h-1。
9. the method according to claim 7 or 8, it is characterised in that the temperature of the reduction is 100-150 DEG C, hydrogen pressure
Power is normal pressure, and hydrogen flowing quantity is 2-15ml/min.g catalyst, and the time is 3-4 hours.
10. according to the method described in any one in claim 7-9, it is characterised in that the drippolene is that diene value is
20-40g iodine/100g oil, and bromine valency is the drippolene raw material of 40-70g bromines/100g oil.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
| CN103100379A (en) * | 2011-11-14 | 2013-05-15 | 中国石油化工股份有限公司 | Production method of titanium oxide-alumina composite |
| CN104415793A (en) * | 2013-08-27 | 2015-03-18 | 天津大学 | Oxygen-modified catalyst carrier, and preparation method and application thereof |
| CN104549328A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing residual oil hydro-demetallization catalyst |
-
2016
- 2016-06-12 CN CN201610408191.4A patent/CN107486201B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
| CN103100379A (en) * | 2011-11-14 | 2013-05-15 | 中国石油化工股份有限公司 | Production method of titanium oxide-alumina composite |
| CN104415793A (en) * | 2013-08-27 | 2015-03-18 | 天津大学 | Oxygen-modified catalyst carrier, and preparation method and application thereof |
| CN104549328A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing residual oil hydro-demetallization catalyst |
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