CN106669787A - Hydrocracking catalyst grading method and catalytic diesel oil hydro-conversion process - Google Patents
Hydrocracking catalyst grading method and catalytic diesel oil hydro-conversion process Download PDFInfo
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Abstract
The invention discloses a hydrocracking catalyst grading method and a catalytic diesel oil hydro-conversion process. The grading method comprises steps as follows: a hydrocracking reactor is equally divided into 2-8 reaction zones in the material flow direction, each reaction zone is filled with a hydrocracking catalyst containing a regenerant, on the basis of the weight of the hydrocracking catalyst, the content of the regenerant in the hydrocracking catalyst is 10wt%-90wt%, and the content of the regenerant in the hydrocracking catalyst in each reaction zone in the material flow direction is gradually increased. The invention further provides the catalytic diesel oil hydro-conversion process including the hydrocracking catalyst grading method. The cracking reactor is filled with catalysts with different reaction properties in a graded manner, so that the hydrogenation selectivity of diesel oil/gasoline components in the conversion process is improved, and the yield of a high-octane gasoline product is increased.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst grading method and catalytic diesel oil hydroconversion process.
Background technology
In recent years, as the country processes the increasingly heaviness of crude quality, the raw material that catalytic cracking is processed also heaviness and in poor quality increasingly, in addition many enterprises are in order to reach the purpose for improving quality of gasoline or propylene enhancing, catalytic cracking unit has been carried out to transform or improve the operating severity of catalytic cracking unit, the quality for causing the product of catalytic cracking, particularly catalytic diesel oil more deteriorates.
To improve the utilization rate of petroleum resources, improve the total quality level of petrol and diesel oil fuel, realize that product blending is optimized and the maximized target of value of the product, meet the domestic novel technique that is hydrocracked to clean fuel increasing need, high aromatics diesel hydro-conversion production high added value naphtha component and low-sulfur cleaning diesel fuel and there is good application prospect.Both at home and abroad researcher has been also carried out substantial amounts of research work.Foreign countries catalytic cracking light cycle oil are converted into the relevant report of ultra-low-sulphur diesel and high octane value gasoline blending component using hydrocracking process technology.Such as：The meeting of nineteen ninety-five NPRA, David A.Pappal et al. are described by Mobil, Akzo
A kind of single-stage hydrocracking technology of Nobel/Nippon Ketjen and M.W.Kellogg companies exploitation.NPRA meetings in 2005, Vasant P. Thakkar et al. describe the LCO UnicrackingTM technologies of Uop Inc.'s exploitation.It is reported that, the catalytic cycle oil ingredient of low value can be converted into high octane gasoline component and fine-quality diesel oil blending component by both the above technology.The technical process is while ensureing that unconverted diesel component is fully hydrogenated with saturation raising diesel product Cetane number, the yield and octane number of gasoline component is a good and bad important indicator of the technology, therefore, how on the premise of diesel quality is ensured, diesel oil/gasoline component hydrogenation selectivity is improved, the key that gasoline products yield is the technology is improved.
Sinopec Fushun Petrochemical Research Institute develops catalytic diesel oil hydro-conversion technology（FD2G）And supporting catalyst.FD2G technologies adopt high temperature, the process conditions of low pressure, while being equipped with high cracking activity, the hydrocracking catalyst of low hydrogenation activity realizes the design object that catalytic diesel oil Efficient Conversion produces high-knock rating gasoline.This technology is showing the characteristics of being different from conventional hydrocracking process during commercial Application：First, compared to other hydrocracking technology processes, FD2G technical processes differ larger in start of run product slates and product quality with design object, gasoline products octane number and gasoline yield are substantially low, its reactivity worth presents the phenomenon for gradually improving in start of run, gradually improves until reaching a preferable metastable level as the duration of runs extends product slates and gasoline product quality.This process is more slow（Typically more than 1 month）The outstanding behaviours on commercial plant is that gasoline product quality is not up to standard in the start of run quite a long time, have impact on the benefit of enterprise, and further run to last stage reaction, reaction condition is harsher, as increasing for coke content all there occurs serious carbon deposit on strong acid and non-strong acid on catalyst, and active metal is assembled, the loss of catalyst activity reactivity worth is serious, therefore, significantly decline from reaction conversion ratio, product slates and product quality, it is impossible to meet reaction and require, at this moment catalyst needs to be regenerated.At present, the regeneration of Cracking catalyst hydrocracking catalyst after the operating of catalytic diesel oil hydroconversion process process is processed, usually more than at a temperature of 400 DEG C of even more highs, the calcination process in air atmosphere, complete the effect of de- charcoal and metal redistribution, so with the removing of carbide, one side catalyst meleic acid amount product can be recovered well, on the other hand, active metal on catalyst completes to disperse again, and the method regenerated catalyst is close in total acid/strong acid distribution with fresh dose.
The reaction process process of catalytic diesel oil hydro-conversion production high-knock rating gasoline is typically catalytic diesel oil raw material and first passes around preatreating reactors hydrodenitrogeneration reaction, then, denitrification reaction generates oil and carries out hydrocracking reaction generation high octane gasoline component into the hydrocracking reactor of back.In catalytic diesel oil hydroconversion process cracker, along the direction of reaction stream, as gasoline component content gradually increases in the intensification reaction stream of reaction depth, diesel component content is gradually reduced.Therefore, reactor is from top to bottom for the percentage contribution of diesel product and gasoline products is gradually changed.In reactor from top to bottom catalyst for diesel oil reaction contribution be gradually reduced, and to gasoline reaction contribution gradually increase.Therefore, for the technical goal of diesel oil/gasoline component selective reaction in realizing catalyst system to reacting cut, preferably course of reaction should be that reactor upper catalyst agent has preferable open loop and hydrogenation saturability, complete open loop, chain rupture and the hydrogenation saturation of diesel oil distillate, improve diesel product Cetane number, increasing gasoline yield product；And reactor lower part is due to being enriched gasoline fraction, in order to the octane number and yield that improve gasoline products then require that catalyst reduces as far as possible the saturability of gasoline fraction and further ring-opening reaction ability.Traditional catalytic diesel oil hydroconversion process cracker single catalyst system cannot meet such reaction requirement, therefore, the technology awaits further perfect.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of hydrocracking catalyst grading method and catalytic diesel oil hydroconversion process, the present invention is by the catalyst of the grading loading differential responses performance in cracker, conversion process diesel oil/gasoline component hydrogenation selectivity is improve, the yield of high octane gasoline products is improve.
The hydrocracking catalyst grading method of the present invention, including following content：Hydrocracking reactor is divided into 2 ~ 8 reaction zones along Flow of Goods and Materials direction, it is preferably divided into 3 ~ 5 reaction zones, hydrocracking catalyst of the filling containing regenerative agent in each reaction zone, on the basis of hydrocracking catalyst weight, regeneration agent content in hydrocracking catalyst is 10wt% ~ 90wt%, it is preferred that 20wt% ~ 70wt%, regeneration agent content in each reaction zone hydrocracking catalyst in Flow of Goods and Materials direction gradually increases, the percentage that regeneration agent content in adjacent reaction area hydrocracking catalyst increases is 5% ~ 40%, preferably 10% ~ 30%；Along Flow of Goods and Materials direction, the hydrocracking catalyst mass ratio containing regenerative agent in adjacent twoth area is 1:8~2:1, preferably 1:1~1:4；The carbon content of the hydrocracking catalyst containing regenerative agent of each reaction zone can be the same or different, it is preferred that the carbon content along the hydrocracking catalyst containing regenerative agent of each reaction zone in Flow of Goods and Materials direction gradually increases, the percentage that adjacent two reaction zone increases is 2% ~ 50%, preferably 5% ~ 30%.
The described hydrocracking catalyst containing regenerative agent has following property：Specific surface area is 200 ~ 500m2/ g, pore volume is 0.25 ~ 0.50ml/g, carbon content 0.5wt% ~ 5wt%, total meleic acid 0.36 ~ 0.80mmol/L of amount, wherein be not more than 0.10mmol/L more than 350 DEG C of strong acid meleic acid amounts, total meleic acid amount with more than 350 DEG C of strong acid contents than 3 ~ 40, it is preferred that 5 ~ 20, more preferably 8 ~ 18；The atomic ratio 0.30 ~ 0.50 of surface Ni and/or Co and Al, the atomic ratio 0.50 ~ 0.80 of surface Mo and/or W and Al.
The preparation method of the hydrocracking catalyst containing regenerative agent, including：
（1）By the hydrocracking catalyst inactivated in catalytic diesel oil hydroconversion process, roasting is 40% ~ 80% to de- charcoal rate in oxygen-containing atmosphere, obtains regenerative agent；
（2）By step（1）The regenerative agent milling of acquisition, and acquisition of the sieving powder that sieves is standby；
（3）By step（2）The powder that sieves, carrier of hydrocracking catalyst material and the mixing of hydrogenation active metals presoma for obtaining, is subsequently adding dilute nitric acid solution and sesbania powder Jing rolling, after extrusion, and in an inert atmosphere high-temperature process, obtains the hydrocracking catalyst containing regenerative agent.
Step（1）Described catalytic diesel oil hydroconversion process refers to that Sinopec Fushun Petrochemical Research Institute develops catalytic diesel oil hydro-conversion technology（FD2G）, general process conditions are as follows：Refining stage operating condition：4.0 ~ 10.0MPa of reaction pressure, 320 ~ 420 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1；Cracking zone operating condition：4.0 ~ 10.0MPa of reaction pressure, 360 ~ 440 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
Step（1）Process raw material in described catalytic diesel oil hydroconversion process as catalytic diesel oil inferior, catalytic diesel oil density is 0.90 ~ 1.0g/cm3, boiling range scope at 180 ~ 400 DEG C, 500 ~ 2000ppm of nitrogen content, 5000 ~ 15000ppm of sulfur content, 60 ~ 90m% of arene content.
Step（1）Described hydrocracking catalyst can be conventional business-like light oil type hydrogen cracking catalyst such as HC-185, HC-190, FC-24, FC-24B etc., or be prepared according to prior art.
Step（1）The hydrocracking catalyst of described inactivation has following property：Specific surface area is 50 ~ 200m2/ g, pore volume is 0.05 ~ 0.2ml/g, carbon content 8wt% ~ 20wt%, 0.05 ~ 0.3mmol/L of total meleic acid amount, wherein being no more than 0.05mmol/L more than 350 DEG C of strong acid meleic acid amounts；The atomic ratio 0.02 ~ 0.10 of surface Ni and/or Co and Al, the atomic ratio 0.12 ~ 0.20 of surface Mo and/or W and Al.
Step（1）Oxygen content 0.5v% ~ the 8v% of described oxygen-containing gas, preferred 2v% ~ 5v%；The oxygen-containing gas is oxygen and CO, CO2、N2, helium, the mixed gas of one or more in neon or argon gas.
Step（1）Described roasting condition is：250 ~ 400 DEG C of sintering temperature, roasting time is 2 ~ 20 hours；The detailed process of general roasting is：Oxygen-containing gas is passed through in regenerating furnace, gas/agent volume ratio 500 is controlled：1~5000：1, while 250 ~ 400 DEG C are warming up to 20 ~ 40 DEG C/h of heating rates, constant temperature calcining 2 ~ 20 hours.
Step（1）The regenerative agent for obtaining has following property：Specific surface area is 200 ~ 350m2/ g, pore volume is 0.20 ~ 0.35ml/g, carbon content 3wt% ~ 8wt%, total meleic acid 0.30 ~ 0.50mmol/L of amount, wherein it is not more than the atomic ratio 0.03 ~ 0.12 of 0.1mmol/L, surface Ni and/or Co and Al, the atomic ratio 0.14 ~ 0.22 of surface Mo and/or W and Al more than 350 DEG C of strong acid meleic acid amounts.
Step（2）The mesh number of the described powder that sieves is generally 50 ~ 300 mesh.
Step（3）The addition of the described powder that sieves is calculated as 20% ~ 70% with final total catalyst weight.
Step（3）Described hydrogenation active metals presoma is hydrogenation active metals salt or oxide, group VIII and/or group vi metallic element generally in the periodic table of elements, wherein group VIII active metal can be Ni and/or Co, group vi active metal is being W and/or Mo, with final overall catalyst weight gauge, addition with hydrogenation active metals oxide count in the final catalyst accounting as 4% ~ 15%.
Step（3）Described carrier of hydrocracking catalyst material generally includes the silica-alumina supports of Y molecular sieve, with final overall catalyst weight gauge, in the final catalyst accounting is 15% ~ 40% to Y molecular sieve addition, and in the final catalyst accounting is 5% ~ 20% for amorphous silica-alumina and/or aluminum oxide addition.
Step（3）Described high-temperature process condition is：Treatment temperature is 400 ~ 700 DEG C, and process time is 2 ~ 10 hours.
Present invention simultaneously provides a kind of catalytic diesel oil hydroconversion process, including herein below：
I, under the conditions of hydrofining technology, the mixed material of catalytic cracking diesel oil and hydrogen is introduced into hydrogenation reactor and Hydrobon catalyst haptoreaction；
II, under the conditions of hydrocracking process, hydrofining reaction effluent be directly entered according to above-mentioned hydrocracking catalyst grading method load hydrocracking reactor, the hydrocracking catalyst bed haptoreaction with grading loading in reactor；
III, step（II）Obtain that hydrocracking reaction effluent is separated and fractionation obtains naphtha component and diesel component, wherein naphtha component directly goes out device as high-knock rating gasoline blend component, diesel component can directly go out device blended diesel, be also recycled into cracker and further react.
Step（I）Described hydrofining technology condition is：4.0 ~ 10.0MPa of reaction pressure, 320 ~ 420 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
Step（I）Described hydrocracking process condition is：4.0 ~ 10.0MPa of reaction pressure, 360 ~ 440 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
Step（I）Process raw material in described catalytic diesel oil hydroconversion process as catalytic diesel oil inferior, catalytic diesel oil density is 0.90 ~ 1.0g/cm3, boiling range scope at 180 ~ 400 DEG C, 500 ~ 2000ppm of nitrogen content, 5000 ~ 15000ppm of sulfur content, 60 ~ 90m% of arene content.
Step（I）Described Hydrobon catalyst can use commercially available prod, it is also possible to be prepared according to this area Conventional wisdom.Hydrobon catalyst used by the present invention can adopt conventional hydrocracking pretreatment catalyst, typically with group vib and/or group VIII metal as active component, with aluminum oxide or silicon-containing alumina as carrier.Vib metals are generally Mo and/or W, and group VIII metal is generally Co and/or Ni.On the basis of the weight of catalyst, vib metals content is calculated as 8wt%～28wt% with oxide, and group VIII tenor is calculated as 2wt%～15wt% with oxide.
The present invention is by x-ray photoelectron power spectrum to catalyst surface Ni（Co）/Al、Mo（W）/ Al atomic ratios carry out characterization test.
In the inventive method, the catalyst surface active metal dispersity recovery rate after regeneration is not less than 80%, more desirably not less than 90%；Catalyst surface active metal dispersity recovery rate=regenerated catalyst decentralization/fresh catalyst decentralization, surface-active metal decentralization is represented with active metal with the atomic ratio of Al.
The inventive method is by x-ray photoelectron power spectrum to catalyst surface Ni（Co）/Al、Mo（W）/ Al atomic ratios carry out characterization test.
The present inventor carries out substantial amounts of research and finds to the hydrocracking catalyst after the operating of FD2G technical process, the gradually improvement of reactivity worth during the process operation, it is relevant with the carbon deposit loss of catalyst runs process strong acid, because catalyst strong acid center is easier carbon deposit, therefore, total meleic acid amount in operation process on catalyst/infrared strong acid amount ratio gradually increases, therefore, so that product slates and gasoline product quality gradually improve, but, at the same time, the decline of strong acid ratio also reduces accordingly the conversion capability of the diesel oil distillate of catalyst, diesel quality is caused to decline.
The present invention regenerates the hydrocracking catalyst for processing using specific process, low concentration oxygen-containing gas low temperature is made charcoal in combination with inert gas high-temperature processing technology, while active metal disperses again in completing reclaimable catalyst, effectively on modulation catalyst strong acid and non-strong acid distribution, so that strong acid/non-strong acid ratio significantly declines on catalyst, catalyst reaction process is significantly improved to polycyclic/mononuclear aromatics hydrogenation and selectivity of ring-opening, more suitable for the reaction of the high petrol content logistics in cracker bottom, so as to improve the technological reaction process diesel oil/gasoline component hydrogenation and cracking reaction selectivity, while diesel product quality is ensured, improve gasoline products octane number and yield.
Hydrocracking catalyst prepared by catalytic diesel oil hydroconversion process cracker filling blending regenerative agent of the present invention, simultaneously, in reactor by under logistics direction, the regenerative agent ratio blended in catalyst gradually increases, the reaction requirement at differential responses position in cracker is so effectively met, the reaction characteristicses of blending different proportion regenerative agent hydrocracking catalyst have been played to greatest extent.The further saturation of the gasoline component of course of reaction open loop, fracture and conversion process generation mainly including diesel oil distillate and open loop in cracker, for this two classes reaction, the open loop of diesel oil distillate, fracture are conducive to improving diesel product Cetane number and increasing gasoline yield, and react the further reaction of the gasoline component for generating then for yield of gasoline and product quality are unfavorable.In the face of this contradiction, conventional single catalyst system cannot be taken into account.And the present inventor's Jing analyses find, the ratio along logistics direction, diesel oil distillate and gasoline fraction in cracker is gradually changed, and gasoline component gradually increases and diesel component is gradually decreased, it may be said that reactor top（Logistics direction from top to bottom）Meet the open loop of diesel oil distillate, hydrogenation reaction with greater need for the higher acidity of catalyst, hydrogenation capability, and bottom diesel component ratio declines, gasoline proportionality rises, accordingly, it would be desirable to reduce catalyst activity and the saturation to gasoline component, cracking reaction.For this purpose, grading distribution scheme of the present invention, gradually steps up the ratio of regenerative agent in catalyst in cracker along logistics direction, using being gradually reduced for catalyst open loop and hydrogenation capability, the selective reaction to diesel oil and gasoline component is realized.
Specific embodiment
Next step further describes the technical characterstic of the present invention by embodiment, but these embodiments can not limit the present invention.
Embodiment 1
（1）Take and be hydrocracked spent agent 1 as in regenerating furnace after certain Industrial Catalysis diesel oil hydrogenation reforming unit operating；
（2）The oxygen/nitrogen mixed gas that oxygen content is 1v% are passed through in regenerating furnace, control gas/agent compares 4000, meanwhile, 380 DEG C are warming up to 25 DEG C/h heating rates, the regenerative agent of embodiment 1, code T -1 are obtained after constant temperature calcining 4h；
Embodiment 2
（1）Take and be hydrocracked spent agent 2 as in regenerating furnace after certain Industrial Catalysis diesel oil hydrogenation reforming unit operating；
（2）The oxygen/nitrogen mixed gas that oxygen content is 3v% are passed through in regenerating furnace, control gas/agent compares 1500, meanwhile, 350 DEG C are warming up to 25 DEG C/h heating rates, the regenerative agent of embodiment 2, code T -2 are obtained after constant temperature calcining 10h
Embodiment 3
（1）Take and be hydrocracked spent agent 3 as in regenerating furnace after certain Industrial Catalysis diesel oil hydrogenation reforming unit operating；
（2）Oxygen/CO that oxygen content is 3v% is passed through in regenerating furnace2Oxygen mixture, control gas/agent compares 1500, meanwhile, 300 DEG C are warming up to 25 DEG C/h heating rates, the regenerative agent of embodiment 3, code T -3 are obtained after constant temperature calcining 15h；
Embodiment 4
（1）Take and be hydrocracked spent agent 4 as in regenerating furnace after certain Industrial Catalysis diesel oil hydrogenation reforming unit operating；
（2）The oxygen/helium mixed gas that oxygen content is 5v% are passed through in regenerating furnace, control gas/agent compares 4000, meanwhile, 320 DEG C are warming up to 35 DEG C/h heating rates, the regenerative agent of embodiment 4, code T -4 are obtained after constant temperature calcining 10h
Comparative example 1
（1）Take and be hydrocracked spent agent 1 as in regenerating furnace after certain Industrial Catalysis diesel oil hydrogenation reforming unit operating；
（2）Air is passed through in regenerating furnace, control gas/agent compares 4000, meanwhile, 460 DEG C are warming up to 25 DEG C/h heating rates, constant temperature calcining 4h obtains the regenerative agent of comparative example 1, numbering B-1；
Comparative example 2
（1）Take and be hydrocracked spent agent 2 as in regenerating furnace after certain Industrial Catalysis diesel oil hydrogenation reforming unit operating；
（2）Air is passed through in regenerating furnace, control gas/agent compares 4000, meanwhile, 500 DEG C are warming up to 25 DEG C/h heating rates, constant temperature calcining 4h obtains the regenerative agent of comparative example 2, numbering B-2；
Embodiment 1 ~ 4 and the reclaimable catalyst of comparative example 1 ~ 2 and fresh dose of physico-chemical property are as shown in table 1.
Embodiment 1 ~ 4 and the regenerated catalyst physico-chemical property of comparative example 1 ~ 2 are as shown in table 2.
Embodiment 5
The regenerative agent T-1 of Example 1 is sieved after crushing with 200 eye mesh screens, take minus sieve 200g to mix with certain industrialization modified Y molecular sieve a 200g, macroporous aluminium oxide 100g, molybdenum oxide 70g and nickel nitrate 90g, addition 3g/100ml dust technology 300ml are rolled, extruded moulding, 120 DEG C are dried 4h, then, 4h being processed as 550 DEG C of constant temperature in nitrogen atmosphere and obtaining the catalyst of embodiment 5, numbering is C-1；
Embodiment 6
The regenerative agent T-1 of Example 1 is sieved after crushing with 200 eye mesh screens, take minus sieve 400g to mix with certain industrialization modified Y molecular sieve a 200g, macroporous aluminium oxide 100g, molybdenum oxide 70g and nickel nitrate 90g, addition 3g/100ml dust technology 300ml are rolled, extruded moulding, 120 DEG C are dried 4h, then, 4h being processed as 600 DEG C of constant temperature in helium atmosphere and obtaining the catalyst of embodiment 6, numbering is C-2；
Embodiment 7
The regenerative agent T-3 of Example 3 is sieved after crushing with 100 eye mesh screens, take minus sieve 600g to mix with certain industrialization modified Y molecular sieve a 200g, macroporous aluminium oxide 100g, molybdenum oxide 70g and nickel nitrate 100g, addition 3g/100ml dust technology 300ml are rolled, extruded moulding, 120 DEG C are dried 4h, then, 4h being processed as 650 DEG C of constant temperature in CO gas atmosphere and obtaining the catalyst of embodiment 7, numbering is C-3；
Embodiment 8
The regenerative agent T-3 of Example 3 is sieved after crushing with 100 eye mesh screens, take minus sieve 1000g to mix with certain industrialization modified Y molecular sieve a 200g, macroporous aluminium oxide 100g, molybdenum oxide 70g and nickel nitrate 100g, addition 3g/100ml dust technology 300ml are rolled, extruded moulding, 120 DEG C are dried 4h, then, 4h being processed as 650 DEG C of constant temperature in CO gas atmosphere and obtaining the catalyst of embodiment 7, numbering is C-4；
Comparative example 3
The regenerative agent T-1 of Example 1 is sieved after crushing with 200 eye mesh screens, take minus sieve 300g to mix with certain industrialization modified Y molecular sieve a 200g, macroporous aluminium oxide 100g, molybdenum oxide 70g and nickel nitrate 90g, addition 3g/100ml dust technology 300ml are rolled, extruded moulding, 120 DEG C are dried 4h, then, 4h being processed as 500 DEG C of constant temperature in air atmosphere and obtaining the catalyst of embodiment 5, numbering is BC-1；
Comparative example 4
Take and sieved with 200 eye mesh screens after the regenerative agent B-1 of comparative example 1 is crushed, take minus sieve 300g to mix with certain industrialization modified Y molecular sieve a 200g, macroporous aluminium oxide 100g, molybdenum oxide 70g and nickel nitrate 90g, addition 3g/100ml dust technology 300ml are rolled, extruded moulding, 120 DEG C are dried 4h, then, 4h being processed as 550 DEG C of constant temperature in nitrogen atmosphere and obtaining the catalyst of comparative example 4, numbering is BC-2；
Embodiment 5 ~ 8 and the catalyst physico-chemical property of comparative example 3 ~ 4 are as shown in table 3.
Embodiment 9
Midget plant comparative evaluation test is carried out.With catalytic diesel oil as reaction raw materials oil, technological process is once passed through using single hop series connection, the pretreatment catalyst that catalyst refining stage is adopted is the widely used FF-36 hydrogenation pretreatment catalysts in this area, cracking zone is from top to bottom divided into respectively 2 or 4 reaction zones, the level being made up of 2 kinds in C-1, C-2, C-3, C-4 of different proportion or 4 kinds of catalyst is loaded with catalyst system, the blending agent prepared with catalyst A, catalyst A and conventional regeneration agent compares explanation embodiment and comparative example catalyst system response difference.Embodiment is listed in 3 ~ table of table 7 with the raw materials used property of comparative example, appreciation condition and evaluation result.
The embodiment of table 1 and comparative example reclaimable catalyst physico-chemical property.
The embodiment 1 ~ 4 of table 2 and the regenerative agent physico-chemical property of comparative example 1 ~ 2.
The embodiment 5 ~ 8 of table 3 and the catalyst physico-chemical property of comparative example 3 ~ 4.
The raw material oil nature of table 4.
The embodiment 4 of table 5 and comparative example operating condition.
The embodiment of table 6 and comparative example evaluating catalyst result.
The embodiment of table 7 and comparative example evaluating catalyst result.
Claims (16)
1. a kind of hydrocracking catalyst grading method, it is characterised in that including following content：Hydrocracking reactor is divided into 2 ~ 8 reaction zones along Flow of Goods and Materials direction, hydrocracking catalyst of the filling containing regenerative agent in each reaction zone, on the basis of hydrocracking catalyst weight, regeneration agent content in hydrocracking catalyst is 10wt% ~ 90wt%, regeneration agent content in each reaction zone hydrocracking catalyst in Flow of Goods and Materials direction gradually increases, and the percentage that the regeneration agent content in adjacent twoth area hydrocracking catalyst increases is 5% ~ 40%；
The wherein described hydrocracking catalyst containing regenerative agent has following property：Specific surface area is 200 ~ 500m2/ g, pore volume is 0.25 ~ 0.50ml/g, carbon content 0.5wt% ~ 5wt%, 0.36 ~ 0.80mmol/L of total meleic acid amount, wherein be not more than 0.10mmol/L more than 350 DEG C of strong acid meleic acid amounts, total meleic acid amount with more than 350 DEG C of strong acid contents than 3 ~ 40；The atomic ratio 0.30 ~ 0.50 of surface Ni and/or Co and Al, the atomic ratio 0.50 ~ 0.80 of surface Mo and/or W and Al.
2. according to the grading method described in claim 1, it is characterised in that：Along Flow of Goods and Materials direction, the hydrocracking catalyst mass ratio containing regenerative agent in adjacent twoth area is 1:8~2:1.
3. according to the grading method described in claim 1, it is characterised in that：Along Flow of Goods and Materials direction, the carbon content of the hydrocracking catalyst containing regenerative agent of each reaction zone gradually increases, and the percentage that adjacent reaction area increases is 2% ~ 50%.
4. according to the grading method described in claim 1, it is characterised in that：The preparation method of the hydrocracking catalyst containing regenerative agent, including：（1）By the hydrocracking catalyst inactivated in catalytic diesel oil hydroconversion process, roasting is 40% ~ 80% to de- charcoal rate in oxygen-containing atmosphere, obtains regenerative agent；（2）By step（1）The regenerative agent milling of acquisition, and acquisition of the sieving powder that sieves is standby；（3）By step（2）The powder that sieves, carrier of hydrocracking catalyst material and the mixing of hydrogenation active metals presoma for obtaining, is subsequently adding dilute nitric acid solution and sesbania powder Jing rolling, after extrusion, and in an inert atmosphere high-temperature process, obtains the hydrocracking catalyst containing regenerative agent.
5. according to the grading method described in claim 4, it is characterised in that：Step（1）The hydrocracking catalyst of described inactivation has following property：Specific surface area is 50 ~ 200m2/ g, pore volume is 0.05 ~ 0.2ml/g, carbon content 8wt% ~ 20wt%, 0.05 ~ 0.3mmol/L of total meleic acid amount, wherein being no more than 0.05mmol/L more than 350 DEG C of strong acid meleic acid amounts；The atomic ratio 0.02 ~ 0.10 of surface Ni and/or Co and Al, the atomic ratio 0.12 ~ 0.20 of surface Mo and/or W and Al.
6. according to the grading method described in claim 4, it is characterised in that：Step（1）Oxygen content 0.5v% ~ the 8v% of described oxygen-containing gas；The oxygen-containing gas is oxygen and CO, CO2、N2, helium, the mixed gas of one or more in neon or argon gas.
7. according to the grading method described in claim 4, it is characterised in that：Step（1）Described roasting condition is：250 ~ 400 DEG C of sintering temperature, roasting time is 2 ~ 20 hours.
8. according to the grading method described in claim 4, it is characterised in that：Step（1）The regenerative agent for obtaining has following property：Specific surface area is 200 ~ 350m2/ g, pore volume is 0.20 ~ 0.35ml/g, carbon content 3wt% ~ 8wt%, total meleic acid 0.30 ~ 0.50mmol/L of amount, wherein it is not more than the atomic ratio 0.03 ~ 0.12 of 0.1mmol/L, surface Ni and/or Co and Al, the atomic ratio 0.14 ~ 0.22 of surface Mo and/or W and Al more than 350 DEG C of strong acid meleic acid amounts.
9. according to the grading method described in claim 4, it is characterised in that：Step（2）The mesh number of the described powder that sieves is generally 50 ~ 300 mesh.
10. according to the grading method described in claim 4, it is characterised in that：Step（3）The addition of the described powder that sieves is calculated as 10% ~ 90% with final total catalyst weight.
11. according to the grading method described in claim 4, it is characterised in that：Step（3）Described hydrogenation active metals presoma is hydrogenation active metals salt or oxide, group VIII and/or group vi metallic element in the periodic table of elements, wherein group VIII active metal is Ni and/or Co, group vi active metal is W and/or Mo, with final overall catalyst weight gauge, addition with hydrogenation active metals oxide count in the final catalyst accounting as 4% ~ 15%.
12. according to the grading method described in claim 4, it is characterised in that：Step（3）Described carrier of hydrocracking catalyst material is the silica-alumina supports for including Y molecular sieve, with final overall catalyst weight gauge, in the final catalyst accounting is 15% ~ 40% to Y molecular sieve addition, and in the final catalyst accounting is 5% ~ 20% for amorphous silica-alumina and/or aluminum oxide addition.
13. according to the grading method described in claim 4, it is characterised in that：Step（3）Described high-temperature process condition is：Treatment temperature is 400 ~ 700 DEG C, and process time is 2 ~ 10 hours.
14. a kind of catalytic diesel oil hydroconversion process, it is characterised in that including herein below：I, under the conditions of hydrofining technology, the mixed material of catalytic cracking diesel oil and hydrogen is introduced into hydrogenation reactor and Hydrobon catalyst haptoreaction；II, under the conditions of hydrocracking process, hydrofining reaction effluent is directly entered the hydrocracking reactor according to the hydrocracking catalyst grading method filling described in claim 1 ~ 13 any claim, the hydrocracking catalyst bed haptoreaction with grading loading in reactor；III, step（II）Obtain that hydrocracking reaction effluent is separated and fractionation obtains naphtha component and diesel component, wherein naphtha component directly goes out device as high-knock rating gasoline blend component, and diesel component directly goes out device blended diesel or loops back cracker and further reacts.
15. according to the technique described in claim 14, it is characterised in that：Step（I）Described hydrofining technology condition is：4.0 ~ 10.0MPa of reaction pressure, 320 ~ 420 DEG C of reaction temperature, 1.0 ~ 4.0h-1 of volume space velocity, hydrogen to oil volume ratio 200：1~2000：1.
16. according to the technique described in claim 14, it is characterised in that：Step（I）Described hydrocracking process condition is：4.0 ~ 10.0MPa of reaction pressure, 360 ~ 440 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
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