CN101121899B - Selectivity hydrogenation method for whole fraction crack petroleum - Google Patents
Selectivity hydrogenation method for whole fraction crack petroleum Download PDFInfo
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- CN101121899B CN101121899B CN200610029962A CN200610029962A CN101121899B CN 101121899 B CN101121899 B CN 101121899B CN 200610029962 A CN200610029962 A CN 200610029962A CN 200610029962 A CN200610029962 A CN 200610029962A CN 101121899 B CN101121899 B CN 101121899B
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003208 petroleum Substances 0.000 title abstract 5
- 239000011148 porous material Substances 0.000 claims abstract description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 230000000737 periodic effect Effects 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000000197 pyrolysis Methods 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 13
- 150000001993 dienes Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 3
- -1 diene hydrocarbon Chemical class 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 229940024548 aluminum oxide Drugs 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000005673 monoalkenes Chemical class 0.000 abstract 1
- 229910003445 palladium oxide Inorganic materials 0.000 abstract 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 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 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000009183 running Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The event relates to a selective hydrogenating method applied to whole-fraction cracked petroleum. The invention is mainly used to settle the problems of existing technology that selective hydrogenation for whole-fraction cracked petroleum containing gummy and free water is difficult. In the invention, C5 hydrocarbon - dry-point takes cracked petroleum prepared by fraction of hydrocarbon compoundunder 204 DEG C, the reaction temperature is 30-80 DEG C, the reaction pressure is 2.0-3.0MPa, the fresh oil airspeed is 2.5-5.0h -1; if the hydrogen/oil volume ratio is 60-120:1, the raw material contacts with the catalyst, the reaction takes place, and the diene hydrocarbon and alkylene arene in the raw material are transformed into mono-olefin and alkyl aromatics; wherein, the catalyst consistsof aluminum-oxide carrier, active component (palladium metal or palladium oxide), at least one IA or IIA element (or the oxydate of IA or IIA) selected from the periodic system of elements, at leastone IVA or VA (or the oxydate of IVA or VA) selected from the periodic system of elements; the ratio of the carrier and the surface area is 40-160m 2/g, the total pore volume is 0.3-1.2ml./g; the technical proposal of composite pore distribution of the carrier can better solve the problem, and can be applied to industrial production of whole-fraction cracked petroleum selective hydrogenation.
Description
Technical field
The present invention relates to a kind of method that is used for the full-cut fraction pyrolysis gasoline selective hydrogenation.
Background technology
The utilization of pyrolysis gasoline is to improve one of main path of device overall economic efficiency in the ethylene unit.Because pyrolysis gasoline is formed complicated, poor heat stability, usually, remove diolefine and vinylbenzene through one-stage selective hydrogenation earlier, after the secondary hydrogenation desulfurization, be mainly used in the aromatic hydrocarbons extracting.It mainly is Pd system or Ni series catalysts with catalyzer that present industrial pyrolysis gasoline is selected hydrogenation, middle runnings (C
6～C
8The hydrocarbon compound cut) hydrogenation or full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) hydrogenation technique.Full-cut fraction pyrolysis gasoline is rich in C
5, C
9 +(carbon nine and more than) unsaturated component, the diene height, easily polymerization, colloid (high molecular polymer that unsaturated component polymerization reaction take place such as diolefine and vinylbenzene generates) height, heavy constituent are many, coke powder content height, stability is poor, lack effective oily water separation means owing to form azeotrope or full scale plant, cause raw material free water content height, poisonous substances such as heavy metal easily are enriched in C
9 +In (carbon nine and more than) cut and characteristics such as the hydrogenation thermal discharge is big, make the very fast inactivation of catalyzer, thereby catalyzer have to frequent activation and regeneration.The Pd/Al of present industrial application
2O
3Catalyzer diene low temperature hydrogenation activity, selectivity, air speed and water-fast etc. anti-interference can performance etc. the aspect have very big gap, be difficult to adapt to the often requirement of fluctuation of pyrolysis gasoline one-stage hydrogenation highly selective, high-speed and raw materials quality in the ethylene industry, therefore, wish that hydrogenation catalyst has better anti-interference, suitable appearance glue ability, higher low temperature active and selectivity, increasing the catalyst regeneration cycle, thereby prolong catalyzer work-ing life.
Chinese patent CN1635054A discloses a kind of catalyzer and preparation method and application that heavy fraction of pyrolysis gasoline is selected hydrogenation that be used for, wherein the alumina catalyst support surface coverage has alkaline-earth metal or its oxide compound of 1～3 weight %, active ingredient is Pd and Mo or Pd and W, Pd content is 0.24～0.35% (weight), and the weight ratio of Pd and Mo or Pd and W is 1: 0.5～2.5.It is said that this catalyzer can be used for pyrolysis gasoline C
5～C
9Cut, particularly C
8～C
9Heavy fractioning hydrogenation has the low temperature active height, and anti-As, S, O, N impurity ability are strong, and charging capacity is big and activity stabilized.But and undeclared its water resistance.
Chinese patent CN1184289C discloses a kind of catalyzer and preparation method and application that pyrolysis gasoline is selected hydrogenation that be used for, comprise titanium dioxide-aluminum oxide mixture as carrier, and be carried on activity component metal palladium on this complex carrier, wherein the content of palladium metal is based on 0.25～0.35% (weight) of described total catalyst weight, it is said that this catalyzer has the air speed height, selectivity and good stability, but not mentioned freedom from jamming, appearance glue ability and water tolerance.
Chinese patent CN1181165A discloses a kind of selective hydrogenation catalyst, is made of 50～150 meters of aluminum oxide specific surfaces 0.15～0.5% (weight) Pd, 0.1～3.0% (weight) alkaline earth metal oxide and alumina catalyst support
2/ gram, 0.35～0.55 milliliter/gram of specific pore volume, the hole of pore radius 5.0～10.0 nanometers accounts for more than 70% of total pore volume.It is said that this catalyzer is not only applicable to the one-stage selective hydrogenation of gasoline splitting process, also is applicable to C
3～C
6Distillate camber unsaturated hydrocarbon selective hydrogenation generates the process of monoolefine.But its low temperature active and selectivity are still waiting further raising.
Summary of the invention
Technical problem to be solved by this invention is to exist in the prior art to be difficult to colloid and the higher full cut (C of free water content
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) pyrolysis gasoline carries out the technical problem of selective hydrogenation. a kind of new method that is used for the full-cut fraction pyrolysis gasoline selective hydrogenation is provided. this method has the low temperature active height, it is strong to hold the glue ability, good stability, and have the good advantage of anti-free-water performance.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that is used for the full-cut fraction pyrolysis gasoline selective hydrogenation, and with C
5Hydrocarbon～do is that the pyrolysis gasoline and the hydrogen of 204 ℃ hydrocarbon compound cut is raw material, is 30～80 ℃ in temperature of reaction, and reaction pressure is 2.0～3.0MPa, and the green oil air speed is 2.5～5.0 hours
-1Hydrogen/oil volume ratio is under 60～120: 1 the condition, raw material contacts with catalyzer, react, diolefin in the raw material and alkylene aromatic component change into monoolefine and alkylaromatic hydrocarbon, and wherein the alumina catalyst support catalyzer comprises following component by weight percentage: (a) 0.01～0.5% palladium metal or its oxide compound; (b) 0.01～2.0% at least a element or its oxide compound that is selected among I A in the periodic table of elements or the IIA; (c) 0.01～20.0% at least a element or its oxide compound that is selected among IVA in the periodic table of elements or the VA; (d) alumina supporter; Described alumina supporter specific surface area is 40～160 meters
2/ gram, total pore volume is 0.3～1.2 a milliliter/gram, and the pore volume of bore dia＜30 nanometers accounts for 5～60% of total pore volume, and the pore volume of bore dia 30～60 nanometers accounts for 20～75% of total pore volume, and the pore volume of bore dia＞60 nanometers accounts for 20～60% of total pore volume; Wherein, the element that is selected from IA in the periodic table of elements is a potassium; The element that is selected from IIA in the periodic table of elements is at least a for being selected from calcium, magnesium or the barium; The element that is selected from IVA in the periodic table of elements is a silicon; The element that is selected from VA in the periodic table of elements is a phosphorus.
In the technique scheme, be 0.1～0.5% with the consumption preferable range of alumina catalyst support weight percent meter palladium metal or its oxide compound; Being selected from least a element among IA in the periodic table of elements or the IIA or the consumption preferable range of its oxide compound is 0.2～0.8%; Being selected from least a element among IVA in the periodic table of elements or the VA or the consumption preferable range of its oxide compound is 0.2～10.0%.Alumina supporter specific surface area preferable range is 50～150 meters
2/ gram, total pore volume preferable range is 0.4～1.0 a milliliter/gram, the pore volume preferable range of bore dia＜30 nanometers is to account for 20～45% of total pore volume, the pore volume preferable range of bore dia 30～60 nanometers accounts for 20～40% of total pore volume, and the pore volume preferable range of bore dia＞60 nanometers is to account for 30～50% of total pore volume.Method of hydrotreating of the present invention is specially adapted to contain the selective hydrogenation of the full-cut fraction pyrolysis gasoline of higher colloid and free-water.In order to obtain higher selectivity, the temperature of reaction preferable range of employing is 30～60 ℃, and the reaction pressure preferable range is 2.5～2.8MPa, and green oil air speed preferable range is 2.5～3.8 hours
-1, hydrogen/oil volume is 80～110: 1 than preferable range.
The preparation method of carrier of the present invention comprise with aluminum oxide and properties-correcting agent, peptizing agent, water mix in the desired amount, behind the extruded moulding, earlier 50～120 ℃ dry 1～24 hour down, then 800～1150 ℃ of following roastings 1～10 hour, obtain alumina supporter.
Preparation of catalysts method of the present invention is identical with common lamella catalyst dipping technique: earlier with a kind of liquid preimpregnation carrier that can dissolve each other with steeping fluid, again with containing the salt solution impregnation of palladium, soaked carrier through washing, dry, 300～600 ℃ of roastings promptly get the oxidative catalyst finished product in air.Finished catalyst only needs to lead to hydrogen reducing and can use in reactor.
The catalyzer that the present invention adopts has composite pore structural, bigger can several apertures, and be rich in abundant mesoporous.Catalyzer of the present invention has good low temperature active, selectivity and stability when being used for the full-cut fraction pyrolysis gasoline selective hydrogenation, and has good freedom from jamming, anti-high colloid and high-content free-water performance.In 40 ℃ of temperature ins, reaction pressure 2.7Mpa, hydrogen/oil volume than 80: 1, green oil air speed 3.8 hours
-1Under the condition, be that 150 milligrams/100 gram oil, free water content are the full cut (C of 1000ppm to gum level
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) pyrolysis gasoline carries out selective hydrogenation reaction, and its outlet diene mean value is 0.0 gram iodine/100 gram oil, and the diolefin hydrogenation rate is 100%, has obtained better technical effect.
The present invention is further elaborated below by embodiment.But these embodiment in no case are construed as limiting scope of the present invention.
Embodiment
[embodiment 1]
Take by weighing pseudo-boehmite 300 grams, 150 gram αYang Hualvs, 9 gram sesbania powder, mix, add afterwards and contain polyvinyl alcohol solution (mass concentration is 5%) 25 grams, nitric acid 4.0 grams, concentration is 85% phosphatase 11 .8 gram, saltpetre 1.5 gram, 360 milliliters of the aqueous solution of magnesium nitrate 2 grams are extruded into the trifolium of 2.5 millimeters of φ, wet bar through 50 ℃ of dryings after 24 hours in 1000 ℃ of roastings 4 hours, obtain having the modified aluminium oxide supports Z1 of composite pore structural.With deionized water preimpregnation carrier, drain away the water then, with carrier at excessive PdCl
2Flood in the steeping fluid, be colourless, drain to steeping fluid, 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours make the catalyst based C1 of Pd, and making final Pd content is 0.3% of alumina catalyst support weight.Catalyzer composition and specific surface, pore volume, pore distribution see Table 1, and wherein each component concentration is all in alumina catalyst support weight.
[embodiment 2]
Employing has the modified aluminium oxide supports Z2 of composite pore structural, and the preparing carriers method is with embodiment 1, and vehicle group becomes to see Table 1.Make the catalyst based C2 of Pd with embodiment 1 same pickling process operation steps and condition, making final Pd content is 0.5% of alumina catalyst support weight.Catalyzer composition and specific surface, pore volume, pore distribution see Table 1, and wherein each component concentration is all in alumina catalyst support weight.
[embodiment 3]
Employing has the modified aluminium oxide supports Z3 of composite pore structural, and the preparing carriers method is with embodiment 1, and vehicle group becomes to see Table 1.Make the catalyst based C3 of Pd with embodiment 1 same pickling process operation steps and condition, making final Pd content is 0.15% of alumina catalyst support weight.Catalyzer composition and specific surface, pore volume, pore distribution see Table 1, and wherein each component concentration is all in alumina catalyst support weight.
[comparative example 1]
Take by weighing pseudo-boehmite 300 gram, 9 gram sesbania powder, 45 gram graphite mix, and are extruded into the trifolium of 2.5 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 1050 ℃ of roastings 4 hours, obtain carrier D1.Make the catalyst based CD1 of Pd with embodiment 1 same operation steps and condition, making final Pd content is 0.3% of alumina catalyst support weight.Catalyzer composition and specific surface, pore volume, pore distribution see Table 1, and wherein each component concentration is all in alumina catalyst support weight.
Table 1
[embodiment 4]
Present embodiment explanation embodiment 1～3 gained catalyzer is at full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) pyrolysis gasoline selects the application in the hydrogenation.
Getting each 100 milliliters of the embodiment of the invention 1～3 catalyzer, is 2.7MPa at hydrogen pressure, and temperature is that 110 ℃ and hydrogen flowing quantity are reduction 8 hours under the 4 milliliters/condition of (decigram catalyzer).At hydrogen pressure 2.7MPa, 40 ℃ of temperature ins, green oil air speed 3.8 hours
-1(total air speed 13.8 hours
-1), feed the full-cut fraction pyrolysis gasoline raw material under the condition of hydrogen/oil volume than 80: 1 and test.Gum level is that 150 milligrams/100 gram oil, free water content are 1000ppm in the full-cut fraction pyrolysis gasoline raw material, and its weight percent consists of C
5Hydrocarbon 15～16%, C
6～C
8Hydrocarbon 63～67%, C
9 +Hydrocarbon 17.7～18.5%, diene value 27.12.Hydrogenation the results are shown in Table 2.
[comparative example 2]
Get comparative example 1 catalyzer CD1100 milliliter, reduce with embodiment 4 same conditions.Test with embodiment 4 same raw material, reaction conditionss, hydrogenation the results are shown in Table 2.
Table 2
[embodiment 5]
1 catalyzer C1 is at full cut (C for the present embodiment explanation embodiment of the invention
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) pyrolysis gasoline selects in the hydrogenation 1000 hours test-results.
Get embodiment 1 catalyzer C1100 milliliter, repeat the reduction process of embodiment 4, in temperature＜45 ℃, reaction pressure 2.65Mpa, green oil air speed 3.8 hours
-1(total air speed 13.8 hours
-1), feed the full-cut fraction pyrolysis gasoline raw material under the condition of hydrogen/oil volume than 80: 1 and test.Gum level is that 150 milligrams/100 gram oil, free water content are 1000ppm in the full-cut fraction pyrolysis gasoline raw material, and its weight percent consists of C
5Hydrocarbon 15～16%, C
6～C
8Hydrocarbon 63～67%, C
9 +Hydrocarbon 17.7～18.5%, diene value 27.12.Hydrogenation the results are shown in Table 3.
Table 3
| During reaction (hour) | The average diene of product (gram iodine/100 gram oil) | Average diolefin hydrogenation rate % |
| 50 | 0.00 | 100.00 |
| 100 | 0.05 | 99.58 |
| 150 | 0.06 | 99.53 |
| 200 | 0.07 | 99.40 |
| 250 | 0.06 | 99.52 |
| 300 | 0.08 | 99.39 |
| 350 | 0.07 | 99.47 |
| 400 | 0.06 | 99.54 |
| 450 | 0.05 | 99.59 |
| 500 | 0.05 | 99.61 |
| 550 | 0.06 | 99.50 |
| 600 | 0.07 | 99.46 |
| 650 | 0.07 | 99.44 |
| 700 | 0.08 | 99.41 |
| 750 | 0.07 | 99.45 |
| 800 | 0.07 | 99.49 |
| 850 | 0.07 | 99.43 |
| During reaction (hour) | The average diene of product (gram iodine/100 gram oil) | Average diolefin hydrogenation rate % |
| 900 | 0.07 | 99.46 |
| 950 | 0.07 | 99.49 |
| 1000 | 0.06 | 99.52 |
[embodiment 6]
1 catalyzer C1 is at full cut (C for the present embodiment explanation embodiment of the invention
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) pyrolysis gasoline selects to change in the hydrogenation test-results of appreciation condition.
Get embodiment 1 catalyzer C1100 milliliter, repeat the reduction process of embodiment 4, feed full-cut fraction pyrolysis gasoline raw material change processing condition and test.Gum level is that 150 milligrams/100 gram oil, free water content are 1000ppm in the full-cut fraction pyrolysis gasoline raw material, and its weight percent consists of C
5Hydrocarbon 15～16%, C
6～C
8Hydrocarbon 63～67%, C
9 +Hydrocarbon 17.7～18.5%, diene value 27.12.Hydrogenation the results are shown in Table 4.
Table 4
Claims (3)
1. method that is used for the full-cut fraction pyrolysis gasoline selective hydrogenation is with C
5Hydrocarbon～do is that the pyrolysis gasoline and the hydrogen of 204 ℃ hydrocarbon compound cut is raw material, is 30～80 ℃ in temperature of reaction, and reaction pressure is 2.0～3.0MPa, and the green oil air speed is 2.5～5.0 hours
-1Hydrogen/oil volume ratio is that raw material contacts with catalyzer, reacts under 60～120: 1 the condition, make diolefin and alkylene aromatic component in the raw material change into monoolefine and alkylaromatic hydrocarbon, wherein catalyzer comprises following component with the alumina catalyst support weight percent meter:
(a) 0.01～0.5% palladium metal or its oxide compound;
(b) 0.01～2.0% at least a element or its oxide compound that is selected among IA in the periodic table of elements or the IIA;
(c) 0.01～20.0% at least a element or its oxide compound that is selected among IVA in the periodic table of elements or the VA;
(d) alumina supporter;
Described alumina supporter specific surface area is 40～160 meters
2/ gram, total pore volume is 0.3～1.2 a milliliter/gram, and the pore volume of bore dia＜30 nanometers accounts for 5～60% of total pore volume, and the pore volume of bore dia 30～60 nanometers accounts for 20～75% of total pore volume, and the pore volume of bore dia＞60 nanometers accounts for 20～60% of total pore volume; Wherein, the element that is selected from IA in the periodic table of elements is a potassium; Be selected from that the element of IIA is selected from calcium, magnesium or the barium at least a in the periodic table of elements; The element that is selected from IVA in the periodic table of elements is a silicon; The element that is selected from VA in the periodic table of elements is a phosphorus.
2. according to the described method that is used for the full-cut fraction pyrolysis gasoline selective hydrogenation of claim 1, it is characterized in that temperature of reaction is 30～60 ℃, reaction pressure is 2.5～2.8MPa, and the green oil air speed is 2.5～3.8 hours
-1, hydrogen/oil volume ratio is 80～110: 1.
3. according to the described method that is used for the full-cut fraction pyrolysis gasoline selective hydrogenation of claim 1, it is characterized in that the consumption of palladium metal or its oxide compound is 0.1～0.5% with the alumina catalyst support weight percent meter; Being selected from least a element among IA in the periodic table of elements or the IIA or the consumption of its oxide compound is 0.2～0.8%; Being selected from least a element among IVA in the periodic table of elements or the VA or the consumption of its oxide compound is 0.2～10.0%; The alumina supporter specific surface area is 50～150 meters
2/ gram; Total pore volume is 0.4～1.0 a milliliter/gram; The pore volume of bore dia＜30 nanometers accounts for 20～45% of total pore volume; The pore volume of bore dia 30～60 nanometers accounts for 20～40% of total pore volume; The pore volume of bore dia＞60 nanometers accounts for 30～50% of total pore volume.
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| CN106994361B (en) * | 2017-06-02 | 2019-07-12 | 钦州学院 | A kind of alumina support and preparation method with macroporous structure |
| CN107189812B (en) * | 2017-06-02 | 2019-01-25 | 钦州学院 | A method for selective hydrogenation of cracked C6-C8 fractions |
| CN107189811B (en) * | 2017-06-02 | 2019-01-25 | 钦州学院 | A kind of one-stage selective hydrogenation method of whole fraction pyrolysis gasoline |
| CN107159279B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of pyrolysis gasoline one-stage selective hydrogenation catalyst and preparation method thereof |
| CN109395717B (en) * | 2017-08-18 | 2021-09-03 | 中国石油化工股份有限公司 | High-efficiency selective hydrogenation catalyst for polycyclic aromatic hydrocarbon |
| CN109364930B (en) * | 2018-10-11 | 2021-07-20 | 东营天喜化工有限公司 | Selective hydrogenation catalyst for pyrolysis gasoline and preparation method thereof |
| CN109321270B (en) * | 2018-10-11 | 2021-06-29 | 泉州市利泰石化科技有限公司 | Selective hydrogenation method for unsaturated hydrocarbons in middle distillate of pyrolysis gasoline |
| CN113694944B (en) * | 2020-05-20 | 2024-06-07 | 中国石油化工股份有限公司 | Palladium selective hydrogenation catalyst for pyrolysis gasoline and preparation method and application thereof |
| CN117654475A (en) * | 2022-08-19 | 2024-03-08 | 中国石油化工股份有限公司 | Macroporous alumina forming carrier, selective hydrogenation catalyst, preparation method and application thereof |
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