CN107304373A - A kind of catalytic diesel oil hydroconversion process - Google Patents
A kind of catalytic diesel oil hydroconversion process Download PDFInfo
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- CN107304373A CN107304373A CN201610252796.9A CN201610252796A CN107304373A CN 107304373 A CN107304373 A CN 107304373A CN 201610252796 A CN201610252796 A CN 201610252796A CN 107304373 A CN107304373 A CN 107304373A
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- molecular sieve
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
Abstract
The invention discloses a kind of catalytic diesel oil hydroconversion process, including herein below：The mixed material of catalytic cracking diesel oil and hydrogen is introduced into hydrogenation reactor and carries out hydrofining reaction, subsequently into cracker, with hydrocracking catalyst bed haptoreaction；Two beds, the hydrocracking catalyst of upper bed layer, with following property above and below wherein being set in hydrocracking reactor：With overall catalyst weight gauge, MoO310%~18%, Co 2%~10%, Modified Zeolite Y 40%~90%, preferably 50~80%, surplus is silica-alumina supports；The hydrocracking catalyst of lower bed layer, with following property：With overall catalyst weight gauge, MoO3Or WO315~30%, NiO2~15%, Modified Zeolite Y 10%~60%, preferably 20%~40%；The filling mass ratio 1 of the hydrocracking catalyst of upper bed layer and lower bed layer：5~5：1.Present invention process improves device liquid on the premise of more preferably catalytic diesel oil conversion ratio is met, further and received, and reduces the hydrogenation saturation of the gasoline component of generation, improves gasoline component octane number.
Description
Technical field
The present invention relates to a kind of hydrocarbon hdyrotreating method, specifically a kind of catalytic diesel oil hydroconversion process.
Background technology
Since the new century, with the increasingly enhancing of people's environmental consciousness, the increasingly strict of national environmental protection regulation and
The fast development of national economy, countries in the world are all being continuously increased to the demand for cleaning automotive fuel.Catalytic cracking（FCC）Technology
It is one of main technique means of heavy oil lighting, important status is all occupied in the oil refining enterprise of countries in the world.I
State's catalytic cracking unit annual working ability alreadys exceed 100,000,000 tons at present, is only second to the U.S..In petrol and diesel oil product composition, catalysis is split
Change gasoline and account for 80% or so, catalytic diesel oil accounts for 30% or so.In recent years, with the domestic increasingly heavy for processing crude quality
Change, the raw material that catalytic cracking is processed also heaviness and in poor quality increasingly, many enterprises are in order to reach improvement quality of gasoline in addition
Or the purpose of propylene enhancing, to catalytic cracking unit transform or improve the operating severity of catalytic cracking unit, led
The product of catalytic cracking is caused, the quality of particularly catalytic diesel oil more deteriorates.
To improve the utilization rate of petroleum resources, the total quality level of petrol and diesel oil fuel is improved, realizes that product blending is optimal
Change and the maximized target of value of the product, meet the country to clean fuel increasing need, high aromatics diesel hydro-conversion
The novel technique that is hydrocracked of production high added value naphtha component and low-sulfur cleaning diesel fuel has before application well
Scape.Domestic and international researcher has also carried out substantial amounts of research work.It is external to be catalyzed using hydrocracking process technology
Cracking light cycle oil is converted into the relevant report of ultra-low-sulphur diesel and high octane value gasoline blending component.Such as：Nineteen ninety-five NPRA
Meeting, David A.Pappal et al. are described by Mobil, Akzo Nobel/Nippon Ketjen and M.W.Kellogg companies
A kind of single-stage hydrocracking technology of exploitation；NPRA meetings in 2005, Vasant P. Thakkar et al. describe UOP
The LCO UnicrackingTM technologies of company's exploitation.It is reported that both the above technology can be by the catalytic cycle oil group of low value
Divide and be converted into high octane gasoline component and fine-quality diesel oil blending component.Yield, the device liquid of the gasoline component of technology production
Receive and octane number is the good and bad important indicator of the technology, therefore, how to reduce gasoline component on the premise of high conversion is ensured
Hydrogenation saturation be the technology key.
US2010116712 discloses a kind of catalytic diesel oil hydrogenating conversion process, and this method is using common process method and splits
Change catalyst, feedstock oil is contacted after first passing around pretreatment with Cracking catalyst, production cleaning diesel oil and high-new alkane value gasoline.But
It is, the hydrogenation saturation for the reduction gasoline component that this method can not be selective, therefore, gasoline products loss of octane number is larger.
EP20110834653 discloses a kind of preparation method of polycyclic aromatic hydrocarbon hydrogenation conversion catalyst, the catalyst carrier
It is made up of beta-molecular sieve and boehmite, vib and group VIII active metal component is added using conventional method, but
Catalyst is same stronger to gasoline component saturability, is unfavorable for catalytic diesel oil hydro-conversion production high-knock rating gasoline process.
The content of the invention
Problem present in high-knock rating gasoline technology is converted into for poor quality catalytic cracking diesel, the invention provides one
Catalytic diesel oil hydroconversion process is planted, on the premise of more preferably catalytic diesel oil conversion ratio is met, device liquid is further improved and receives, drop
The hydrogenation saturation of the gasoline component of low generation, improves gasoline component octane number.Heretofore described silica alumina ratio is SiO2/Al2O3
Mol ratio.
The catalytic diesel oil hydroconversion process of the present invention, including herein below：The mixture of catalytic cracking diesel oil and hydrogen
Material is introduced into hydrogenation reactor, and progress hydrofining reaction is contacted with Hydrobon catalyst, and hydrofining reaction effluent enters
Enter cracker, progress hydrocracking reaction contacted with the hydrocracking catalyst bed of grading loading in cracker,
Hydrocracking reaction effluent obtains naphtha component and diesel component through separating and being fractionated, and wherein naphtha component directly goes out dress
Put as high-knock rating gasoline blend component, diesel component can directly go out device blended diesel, or be recycled back to cracker
Single step reaction；Two beds above and below wherein being set in hydrocracking reactor, the hydrocracking catalyst of upper bed layer, tool
There is following property：With overall catalyst weight gauge, MoO3 10%~18%, CoO 2%~10%, modified Y molecular sieve 40%~90%, preferably
50~80%, surplus is silica-alumina supports；The hydrocracking catalyst of lower bed layer, with following property：With overall catalyst weight gauge,
MoO3 Or WO315%~30%, NiO 2%~15%, Modified Zeolite Y 10%~60%, preferably 20%~40%；Upper bed layer and leave the bed
The filling mass ratio 1 of the hydrocracking catalyst of layer：5~5：1, preferably 1：2~2：1.
In present invention process, the Hydrobon catalyst of selection and it is hydrocracked cracking agent and can uses commercially available prod,
It can be prepared according to this area Conventional wisdom.Hydrobon catalyst used in the present invention can use conventional hydrocracking pretreatment
Catalyst, typically using group vib and/or group VIII metal as active component, using aluminum oxide or silicon-containing alumina as carrier.The
Group vib metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.On the basis of the weight of catalyst, the
Group vib tenor is calculated as 8wt%~28wt% with oxide, and group VIII tenor is calculated as 2wt%~15wt% with oxide.
In present invention process, described silica-alumina supports are amorphous silica-alumina and/or aluminum oxide commonly used in the art.
The modified Y molecular sieve that present invention process is used can be conventional method modified Y molecular sieve, modified Y molecular sieve property
It is as follows：Silica alumina ratio 8 ~ 50, preferably 10 ~ 30；500~900m of specific surface area2/ g, preferably 600~800m2/g；Pore volume 0.30~
0.60ml/g, preferably 0.35~0.50ml/g of pore volume；Relative crystallinity 80%~130%, preferably 90%~110%, cell parameter
2.432~2.460, preferably 2.435~2.450；Meleic acid 0.4~1.5mmol/g of amount, preferably 0.5 ~ 1.3 mmol/g.
The hydrocracking catalyst of upper bed layer in the hydrocracking reactor of the present invention, it is preferred to use Y points of following modification
Son sieve, with following property：Body phase silica alumina ratio（The overall silica alumina ratio of molecular sieve）For 8 ~ 30, wherein top layer silica alumina ratio 20 ~ 100,
It is preferred that 30 ~ 80, superficial layer silica alumina ratio is higher than body phase silica alumina ratio 20 ~ 70, wherein described top layer refers to molecular sieve outer surface to inside
10 ~ 200nm thickness range, more preferably 50 ~ 190nm；Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Sodium oxide molybdena matter
Measure percentage composition and be less than 1.0%；600 ~ 900m of modified Y molecular sieve specific surface area2/ g, preferably 650 ~ 850m2/g；Pore volume 0.20 ~
0.70ml/g, preferably 0.3 ~ 0.6ml/g；Infrared 0.3 ~ 1.5mmol/g of acid content, preferably 0.4 ~ 1.2mmol/g；Relative crystallinity
60% ~ 130%, preferably 70% ~ 120%.
Wherein, the hydrocracking catalyst of upper bed layer uses the preparation method of modified Y molecular sieve in hydrocracking reactor,
Including：（1）The Y molecular sieve synthesized in conventional manner is that former powder carries out Ammonium Salt Ionic exchange in ammonium salt aqueous solution；（2）To step
（1）In obtained ammonium exchange after Y molecular sieve carry out the dealuminzation or dealumination complement silicon of either shallow；（3）To step（2）Y points after processing
Sub- sieve is handled with aluminum salt solution, is dried；（4）By liquid or gaseous unsaturated olefin and step（3）The Y molecular sieve of acquisition is abundant
Contact, then carries out carbon deposit reaction in oxygen-containing atmosphere；（5）By step（4）At the carbon deposit Y molecular sieve quick high-temp roasting of preparation
Reason；（6）By step（5）Obtained molecular sieve carries out deep sealumination modified processing；（7）Step（6）The Y molecular sieve of acquisition is through filtering, doing
After dry, processing of making charcoal is carried out, modified Y molecular sieve is obtained.
Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：Using NaY zeolite as raw material, wherein in NaY molecular sieve
SiO2/Al2O3Mol ratio is 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Wherein ammonium salt be ammonium chloride, ammonium nitrate, ammonium sulfate,
One or more in ammonium acetate or ammonium oxalate, ammonium salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0 ~ 3.0 mol/L,
Exchanged at 60 ~ 120 DEG C, preferably 60 ~ 90 DEG C, swap time is 1 ~ 3 hour, exchange times are 1 ~ 4 time, after finally being exchanged
NaY zeolite Na2O content is less than 3.0%.
Step（2）The either shallow dealuminzation or dealumination complement silicon process are one during hydro-thermal process, acid treatment, ammonium fluosilicate
Plant or several：Wherein, step is worked as（2）During for hydrothermal treatment process, treatment temperature be 400 ~ 600 DEG C, pressure be 0.01 ~
0.5MPa, processing time is 1.0 ~ 4.0 hours；Work as step（2）During for acid treatment process, the acid used in it is sulfuric acid, hydrochloric acid, nitre
One or more in acid, citric acid, oxalic acid or acetic acid, acid solutions are with H+It is calculated as 0.1 ~ 0.7mol/L；Acid solution is with dividing
Son sieve is according to the solid mass ratio 3 of liquid:1~30:1 mixing；30 ~ 80 DEG C for the treatment of temperature, processing time is 0.5 ~ 3h；Work as step（2）For fluorine
During ammonium silicate dealumination complement silicon process, detailed process is：Y molecular sieve, which adds water, is made into the water sample mixing of the solid mass ratio 3 ~ 6 of liquid, then, plus
Enter concentration to handle 0.5 ~ 2 hour in 50 ~ 80 DEG C for 0.3 ~ 1.2mol/L ammonium fluosilicates aqueous solution.
Step（3）Aluminium salt used in described aluminium salt processing procedure be one kind in aluminium chloride, aluminum sulfate or aluminum nitrate or
It is several；Aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and processing time is 0.5 ~ 3 hour.
Step（3）Described drying condition is：100 ~ 400 DEG C of drying temperature, 0.5 ~ 4h of drying time.
Step（4）Described unsaturated olefin is alkene, the alkadienes of the positive structure that carbon number is 2 ~ 10 or isomery；Wherein
Described alkene is fully contacted with molecular sieve refers to that unsaturated hydrocarbons is diffused into inside molecular sieve, if from liquid unsaturated hydrocarbons,
Molecular sieve answers thorough impregnation in liquefied olefines.
Step（4）Described oxygen-containing atmosphere is air, the mixture or oxygen of oxygen and nitrogen and the mixing of inert gas
One kind in thing, the volume fraction of oxygen in the gas phase is 10% ~ 100%, preferably air；Carbon deposit reaction condition is：Reaction temperature
50 ~ 500 DEG C of degree, preferably 100 ~ 400 DEG C, the reaction time is 1 ~ 50 hour, preferably 2 ~ 40 hours.
Step（5）Described quick high-temp calcination process process is：The Y molecular sieve of carbon deposit is directly added into and is warming up in advance
400 ~ 600 DEG C of Muffle kiln roasting 5 ~ 300 minutes, preferably 5-60 minutes.
Step（6）Described in deep sealumination modified processing procedure can be acid treatment or ammonium fluosilicate processing, work as step（6）For
During acid treatment process, the acid used can be the one or more in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid；Acid
Solution concentration is with H+It is calculated as 0.2 ~ 2mol/L；Acid solution is with molecular sieve according to the solid mass ratio 3 of liquid:1~30:1 mixing, treatment temperature
60 ~ 120 DEG C, processing time is 0.5 ~ 3h；Work as step（6）During for ammonium fluosilicate processing procedure, detailed process is generally：By Y points
Son sieve, which adds water, is made into the water sample mixing of the solid mass ratio 3 ~ 6 of liquid, then, add concentration be 0.8 ~ 2mol/L ammonium fluosilicates aqueous solution in
70 ~ 100 DEG C are handled 1 ~ 4 hour.
Step（7）Described treatment conditions of making charcoal are：It is calcined 2 ~ 4 hours, is remained on removing molecular sieve at 400 ~ 600 DEG C
Carbon deposit.
In present invention process, the process conditions of described hydrofining reaction are：Reaction temperature is 320~440 DEG C, preferably
340~420 DEG C；Reaction pressure is 4.0~15.0MPa, preferably 6.0~12.0MPa；Volume space velocity is 0.2~6.0h during liquid-1,
It is preferred that 0.5~3.0h-1；Hydrogen to oil volume ratio is 100~2000, preferably 500~1500.
In present invention process, the process conditions of described hydrocracking reaction are：Reaction temperature is 340~440 DEG C, preferably
360~430 DEG C；Reaction pressure is 4.0~15.0 MPa, preferably 6.0~12.0 MPa；Volume space velocity is 0.2~6.0h during liquid-1, preferably 0.5~3.0h-1；Hydrogen to oil volume ratio is 100~2000, preferably 500~1500.
In present invention process, the property of the catalytic cracking diesel oil is generally：Density is 0.88~0.99g/cm3, it is done
Generally 360~400 DEG C of point, arene content is generally 50wt%~95wt%.The sulfur content of catalytic cracking diesel oil is generally
0.2wt%~2wt%, nitrogen content is 500~2000ppm.
Present invention process has the following advantages that compared with prior art：
Catalytic diesel oil hydro-conversion technology production gasoline component composition is mainly mononuclear aromatics, monocyclic naphthenes and alkane.Its
Paraffin and monocyclic naphthenes are low octane rating component.The main saturation including mononuclear aromatics in the source of monocyclic naphthenes and double
The ring-opening reaction of ring cycloalkane；The source of alkane can be then that the chain-breaking reaction or polycyclic aromatic hydrocarbon of original alkyl-substituted aromatic hydrocarbon are opened
Chain rupture is produced ring again.From the point of view of reaction angle, high gasoline yield, the open loop chain rupture of the cycloalkanes aromatic hydrocarbons of hydrogenation saturation generation are realized
And original alkyl-substituted aromatic hydrocarbon chain rupture is difficult to avoid in raw material, therefore, the reduction potentiality of product paraffin are little.For list
Ring cycloalkane is reduced, then needs while cracking rate is ensured, to reduce the saturation of mononuclear aromatics.Therefore, cracking and hydrogenation are improved
The selectivity of saturated reaction is to improve the key of gasoline component octane number.There is following spy in the cracker on commercial plant
Point：Cracking zone top reaction temperature is general between 360 ~ 380 DEG C, and such temperature is conducive to playing the hydrogenation saturation of catalyst
Ability, therefore, the too high hydrogenation activity of top cracking agent will promote aromatic hydrocarbons saturated reaction, be unfavorable for improving gasoline component octane
Value.And bottom bed reaction temperature typically can reach 400 DEG C, such temperature causes aromatic hydrocarbons saturated reaction to be limited by thermodynamical equilibrium
System, is unfavorable for carrying out hydrogenation saturated reaction, meanwhile, the too high reaction temperature of lower floor also causes cracking excessively, to increase gasoline component
Second pyrolysis, reduces gasoline component yield, produces a large amount of gas components.Therefore, it is hydrocracked and the choosing of aromatic hydrocarbons saturation from raising
Selecting property angle considers that the present invention loads low hydrogenation activity/high cracking activity catalyst on cracking zone top, so that go to bed
Layer catalyst hydrogenation ability is weaker, even in be relatively adapted under the process conditions of aromatic hydrocarbons saturation also will not supersaturation, meanwhile, go to bed
The higher cracking activity of layer, which is also increased, urges bavin conversion ratio to generate more gasoline components.
In addition, the inventive method carries out dealumination treatment by selectivity to the Y molecular sieve outer surface in the cracking agent of top,
The silica alumina ratio of Y molecular sieve outer surfaces is improved, the hydrocracking catalyst prepared compared to conventional method modified molecular screen can be with
It is hydrocracked improving catalyst reaction activity in the case of keeping close anti-nitrogen ability or being improved on the premise of identical activity
The anti-nitrogen ability of catalyst, is also more applicable for the high nitride reaction environment in top, meets high resistance to nitrogen ability and high reaction activity
Reaction requirement；In addition, selectivity to Y molecular sieve outer surface dealumination treatment, add the secondary hole number of molecular sieve outer surface,
Be conducive to macromolecular raw material in the diffusion of the haptoreaction of molecular sieve surface and a pyrolysis product, it is to avoid excessive second pyrolysis hair
It is raw, improve liquid yield.And cracking pars infrasegmentalis can then load high hydrogenation activity/low cracking activity catalyst, due to lower floor's mistake
High reaction temperature, even if also being difficult to play aromatic hydrocarbons saturability using the cracking agent of high hydrogenation activity, and high hydrogenation activity is then
Be conducive to C+The terminating reaction of ion, with reference to the weaker cracking activity of lower floor, reduces gasoline component secondary cracking, improves vapour
Oily yield.
Embodiment
Below by embodiment, the present invention is further described, but is not so limited the present invention.It is described in the inventive method
Body phase silica alumina ratio measured using chemical analysis.Top layer silica alumina ratio uses transmission electron microscope X-ray electronic spectroscopy
Measure.
Embodiment 1
The preparation method of molecular sieve 1 and physico-chemical property：
（1）The former powder 200g of NaY molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 1.5mol/L with concentration is according to liquid-solid ratio 4:1
Mixing, 80 DEG C exchange 2 hours, repeat this process 2 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 2.5%；
（2）To step（1）560 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1MPa；
（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 5:1 mixes with distilled water stirring, 75 DEG C is then heated to, in stirring
During add 0.6mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours.
（4）First by step（3）The dry 3h of 120 DEG C of gained molecular sieve, then, takes hexadiene soaking step（3）Point of gained
Son sieve 2 hours, then, is heated 4 hours in air atmosphere at 150 DEG C；
（5）Step（4）Molecular sieve after processing, which is directly placed into, to be previously heated in 450 DEG C of Muffle furnace, is calcined 10 minutes；
（6）Step（5）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, and it is 0.8mol/L's to add concentration
Ammonium fluosilicate solution 100ml, 95 DEG C are handled 2 hours；
（7）Through step（6）After Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, 550 DEG C of roastings 2 hours, acquisition
Molecular sieve 1 used in embodiment.The transmission electron microscope EDAX results of gained molecular sieve 1 determine its outer surface to 80nm thickness, surface
Layer silica alumina ratio is 42, and molecular sieve body phase silica alumina ratio is 11.5.XRD analysis result shows that its lattice constant is 2.441, relative crystallization
Degree 96%.Pore volume 0.36ml/g, specific surface area 740m2/ g, it is 0.90mmol/g that infrared analysis result, which determines Y-1 meleic acids amount,.
Embodiment 2
The modification process of molecular sieve 2：
（1）The former powder 200g of NaY molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 0.6mol/L with concentration is according to liquid-solid ratio 3:1
Mixing, 80 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 2.0%；
（2）To step（1）530 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1Mpa；
（3）Step（2）Sieve is according to liquid-solid ratio 8:1 and 0.5mol/L oxalic acid solution（Concentration is with H+Meter）400ml is mixed, Ran Housheng
Temperature is to 50 DEG C, isothermal reaction 2 hours；
（4）Step（3）Gained molecular sieve is according to liquid-solid ratio 5:1 mixes with distilled water stirring, 80 DEG C is then heated to, in stirring
During add 0.5mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours.
（5）Step（4）The dry 9h of 100 DEG C of gained molecular sieve；
（6）Take hexadiene soaking step（5）The molecular sieve of gained 3 hours, then, 150 DEG C are heated 25 hours in air atmosphere；
（7）Step（6）Molecular sieve after processing, which is directly placed into, to be previously heated in 400 DEG C of Muffle furnace, is calcined 35 minutes；
（8）Step（7）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, and addition concentration is 1.0 mol/L
Ammonium fluosilicate solution 100ml, 75 DEG C are handled 2 hours；
（9）Through step（8）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours after 550 DEG C are calcined 2 hours, are obtained
Molecular sieve 2.
The transmission electron microscope EDAX results of molecular sieve 2 determine its outer surface to 140nm thickness, and superficial layer silica alumina ratio is 50,
Molecular sieve body phase silica alumina ratio is 20.XRD analysis result shows that its lattice constant is 2.434, relative crystallinity 97%.Pore volume 0.38
Ml/g, specific surface area 680m2/ g, it is 0.66mmol/g that infrared analysis result, which determines Y-2 meleic acids amount,.
Embodiment 3
The preparation method of molecular sieve 3 and physico-chemical property：
Y molecular sieve uses conventional method modification, that is, takes NaY molecular sieve ammonium first to exchange to Na2O content 2.0%, then, with
0.10mol/L ammonium fluosilicate solutions are according to liquid-solid ratio 10:1 mixing is warming up to after 80 DEG C, isothermal reaction 2h, ammonium fluosilicate processing
Afterwards, sample hydro-thermal process 2h at a temperature of 0.1Mpa, 540 DEG C after filtering, washing obtains molecular sieve 3.The silica alumina ratio of molecular sieve 3 is
15.0.XRD analysis result shows that its lattice constant is 2.442, relative crystallinity 92%.Pore volume 0.36ml/g, infrared analysis result
It is 0.93mmol/g to determine meleic acid amount.
Embodiment 4
The preparation method of catalyst 1 and physico-chemical property：
（1）Take the 70g of molecular sieve 1 to prepare macroporous aluminium oxide with 30g conventional methods to mix, add 4g/100ml dust technologies in mixing
Mixing is rolled to extrudable shape in device, and extruded moulding obtains carrier T-1 on banded extruder；
（2）T-1 is taken to be impregnated in Mo-Co active metal maceration extracts, impregnated sample obtains catalyst after drying, roasting, numbers
For C-1.Catalyst pore volume 0.40ml/g, specific surface area 430m2/ g, MoO315wt%, CoO 5wt%.
Embodiment 5
The preparation method of catalyst 2 and physico-chemical property：
（1）Take the 30g of molecular sieve 1 to prepare macroporous aluminium oxide with 70g conventional methods to mix, add 4g/100ml dust technologies in mixing
Mixing is rolled to extrudable shape in device, and extruded moulding obtains carrier T-2 on banded extruder；
（2）T-2 is taken to be impregnated in W-Ni active metal maceration extracts, impregnated sample obtains catalyst after drying, roasting, numbers
For C-2.Catalyst pore volume 0.42ml/g, specific surface area 300m2/ g, WO320wt%, NiO 6wt%.
Embodiment 6
The preparation method of catalyst 3 and physico-chemical property：
（1）Take the 70g of molecular sieve 3 to prepare macroporous aluminium oxide with 30g conventional methods to mix, add 4g/100ml dust technologies in mixing
Mixing is rolled to extrudable shape in device, and extruded moulding obtains carrier T-3 on banded extruder；
（2）T-3 is taken to be impregnated in Mo-Co active metal maceration extracts, impregnated sample obtains catalyst after drying, roasting, numbers
For C-3.Catalyst pore volume 0.39ml/g, specific surface area 420m2/ g, MoO315wt%, CoO 5wt%；
Embodiment 7
Evaluation test is carried out on midget plant, evaluating apparatus is connected using single hop and once produces gasoline and hydrogenation by flow
Diesel oil, an anti-filling conventional hydro catalyst for refining, two anti-filling C1-C3 hydrocracking catalysts respectively, catalyst for refining reason
Change property, raw material oil nature and evaluation result and be listed in table 1 ~ 4.
The anti-catalyst for refining physicochemical property of table 1 one.
The raw material oil nature of table 2.
The type of feed and operating condition of the anticatalyst of table 3 two.
The product of table 4 is distributed and property contrast.
Claims (14)
1. a kind of catalytic diesel oil hydroconversion process, it is characterised in that including herein below：Catalytic cracking diesel oil and hydrogen it is mixed
Compound material is introduced into hydrogenation reactor, and progress hydrofining reaction, hydrofining reaction outflow are contacted with Hydrobon catalyst
Thing enters cracker, and contacting progress with the hydrocracking catalyst bed of grading loading in cracker is hydrocracked instead
Should, hydrocracking reaction effluent obtains naphtha component and diesel component through separating and being fractionated, and wherein naphtha component is direct
Go out device as high-knock rating gasoline blend component, diesel component can directly go out device blended diesel, or be recycled back to cracking reaction
Device further reacts；Two beds, the hydrocracking catalyst of upper bed layer above and below wherein being set in hydrocracking reactor
Agent, with following property：With overall catalyst weight gauge, MoO3 10%~18%, CoO 2%~10%, modified Y molecular sieve 40%~
90%, surplus is silica-alumina supports；The hydrocracking catalyst of lower bed layer, with following property：With overall catalyst weight gauge, MoO3
Or WO315%~30%, NiO 2%~15%, Modified Zeolite Y 10%~60%；The hydrocracking catalyst of upper bed layer and lower bed layer
The filling mass ratio 1 of agent：5~5：1.
2. according to the technique described in claim 1, it is characterised in that：Hydrobon catalyst used is with group vib and/or
Group VIII metal is active component, using aluminum oxide or silicon-containing alumina as carrier；Vib metals are Mo and/or W, VIII
Race's metal is Co and/or Ni；On the basis of the weight of catalyst, vib metals content with oxide be calculated as 8wt%~
28wt%, group VIII tenor is calculated as 2wt%~15wt% with oxide.
3. according to the technique described in claim 1, it is characterised in that：Modified Y molecular sieve property is as follows：Silica alumina ratio 8 ~ 50, compares table
500~900m of area2/ g, 0.30~0.60ml/g of pore volume, relative crystallinity 80%~130%, cell parameter 2.432~2.460,
0.4~1.5mmol/g of meleic acid amount.
4. according to the technique described in claim 1, it is characterised in that：The hydrocracking catalyst of upper bed layer in hydrocracking reactor
Agent, the modified Y molecular sieve of use has following property：Body phase silica alumina ratio is 8 ~ 30, wherein top layer silica alumina ratio 20 ~ 100, superficial layer
Silica alumina ratio is higher than body phase silica alumina ratio 20 ~ 70, wherein described top layer refers to molecular sieve outer surface to 10 ~ 200nm of inside thickness model
Enclose；Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Sodium oxide molybdena weight/mass percentage composition is less than 1.0%；Modified Y molecular sieve
600 ~ 900m of specific surface area2/ g, pore volume 0.20 ~ 0.70ml/g, infrared 0.3 ~ 1.5mmol/g of acid content, relative crystallinity 60% ~
130%。
5. according to the technique described in claim 4, it is characterised in that：The hydrocracking catalyst of upper bed layer in hydrocracking reactor
Agent uses the preparation method of modified Y molecular sieve, including：（1）The Y molecular sieve synthesized in conventional manner is former powder in ammonium salt aqueous solution
Middle progress Ammonium Salt Ionic exchange；（2）To step（1）In obtained ammonium exchange after Y molecular sieve carry out the dealuminzation or dealuminzation of either shallow
Mend silicon；（3）To step（2）Y molecular sieve after processing is handled with aluminum salt solution, is dried；（4）By liquid or gaseous ethylenic unsaturation
Hydrocarbon and step（3）The Y molecular sieve of acquisition is fully contacted, and carbon deposit reaction is then carried out in oxygen-containing atmosphere；（5）By step（4）System
Standby carbon deposit Y molecular sieve quick high-temp calcination process；（6）By step（5）Obtained molecular sieve carries out deep sealumination modified processing；（7）
Step（6）The Y molecular sieve of acquisition carries out processing of making charcoal, obtains modified Y molecular sieve after filtering, drying.
6. according to the technique described in claim 5, it is characterised in that：Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：With
NaY zeolite is raw material, wherein SiO in NaY molecular sieve2/Al2O3Mol ratio is 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Its
Middle ammonium salt is the one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution concentration 0.3 ~
6.0mol/L, is exchanged at 60 ~ 120 DEG C, and swap time is 1 ~ 3 hour, the NaY zeolite Na after finally being exchanged2O content is small
In 3.0%.
7. according to the technique described in claim 5, it is characterised in that：Step（2）The either shallow dealuminzation or dealumination complement silicon process are
One or more during hydro-thermal process, acid treatment, ammonium fluosilicate：Wherein, step is worked as（2）During for hydrothermal treatment process, place
It is 400 ~ 600 DEG C to manage temperature, and pressure is 0.01 ~ 0.5MPa, and processing time is 1.0 ~ 4.0 hours；Work as step（2）To be acid-treated
Cheng Shi, the acid used in it is the one or more in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid, and acid solutions are with H+It is calculated as 0.1 ~ 0.7mol/L；Acid solution is with molecular sieve according to the solid mass ratio 3 of liquid:1~30:1 mixing；30 ~ 80 DEG C for the treatment of temperature, place
The reason time is 0.5 ~ 3h；Work as step（2）During for ammonium fluosilicate dealumination complement silicon process, detailed process is：Y molecular sieve, which adds water, is made into liquid
Gu the water sample mixing of mass ratio 3 ~ 6, then, it is that 0.3 ~ 1.2mol/L ammonium fluosilicates aqueous solution is handled in 50 ~ 80 DEG C to add concentration
0.5 ~ 2 hour.
8. according to the technique described in claim 5, it is characterised in that：Step（3）Aluminium salt used in described aluminium salt processing procedure
It is the one or more in aluminium chloride, aluminum sulfate or aluminum nitrate；Aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120
DEG C, processing time is 0.5 ~ 3 hour.
9. according to the technique described in claim 5, it is characterised in that：Step（3）Described drying condition is：Drying temperature 100 ~
400 DEG C, 0.5 ~ 4h of drying time.
10. according to the technique described in claim 5, it is characterised in that：Step（4）Described unsaturated olefin is that carbon number is
2 ~ 10 positive structure or alkene, the alkadienes of isomery；Wherein described alkene is fully contacted with molecular sieve refers to that unsaturated hydrocarbons spreads
Into inside molecular sieve, if from liquid unsaturated hydrocarbons, molecular sieve thorough impregnation is in liquefied olefines.
11. according to the technique described in claim 5, it is characterised in that：Step（4）Described oxygen-containing atmosphere be air, oxygen with
One kind in the mixture or oxygen of nitrogen and the mixture of inert gas, the volume fraction of oxygen in the gas phase be 10% ~
100%；Carbon deposit reaction condition is：50 ~ 500 DEG C of reaction temperature, the reaction time is 1 ~ 50 hour.
12. according to the technique described in claim 5, it is characterised in that：Step（5）Described quick high-temp calcination process process
For：The Y molecular sieve of carbon deposit is directly added into and is warming up to 400 ~ 600 DEG C of Muffle kiln roasting 5 ~ 300 minutes in advance.
13. according to the technique described in claim 5, it is characterised in that：Step（6）Described in deep sealumination modified processing procedure be acid
Processing or ammonium fluosilicate processing；Work as step（6）During for acid treatment process, the acid used is sulfuric acid, hydrochloric acid, nitric acid, citric acid, grass
One or more in acid or acetic acid；Acid solutions are with H+It is calculated as 0.2 ~ 2mol/L；Acid solution is with molecular sieve according to liquid stereoplasm
Amount compares 3:1~30:1 mixing, 60 ~ 120 DEG C for the treatment of temperature, processing time is 0.5 ~ 3h；Work as step（6）It is treated for ammonium fluosilicate
Cheng Shi, detailed process is：Y molecular sieve is added water and is made into the water sample mixing of the solid mass ratio 3 ~ 6 of liquid, then, add concentration be 0.8 ~
The 2mol/L ammonium fluosilicates aqueous solution is handled 1 ~ 4 hour in 70 ~ 100 DEG C.
14. according to the technique described in claim 5, it is characterised in that：Step（7）Described treatment conditions of making charcoal are：400~600
It is calcined 2 ~ 4 hours at DEG C, the carbon deposit remained on removing molecular sieve.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019104543A1 (en) * | 2017-11-29 | 2019-06-06 | 中国石油化工股份有限公司 | Modified y-type molecular sieve and preparation method therefor, hydrocracking catalyst and preparation method therefor, and method for hydrocracking hydrocarbon oil |
| CN110938467A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Hydrocracking method |
| CN110938468A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Hydrocracking process |
| US11518684B2 (en) | 2018-05-28 | 2022-12-06 | China Petroleum & Chemical Corporation | NaY molecular sieve with an aluminum-rich surface and a process of preparing same |
| RU2792150C2 (en) * | 2018-05-28 | 2023-03-17 | Чайна Петролеум Энд Кемикал Корпорейшн | NaY MOLECULAR SIEVE WITH ALUMINUM-ENRICHED SURFACE AND ITS PRODUCTION METHOD |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100116712A1 (en) * | 2008-11-10 | 2010-05-13 | Bart Dziabala | Combination of mild hydrotreating and hydrocracking for making low sulfur diesel and high octane naphtha |
| CN102311795A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Hydrogenation method for producing high-octane gasoline components by diesel oil raw material |
| CN102463147A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Medium oil type hydrocracking catalyst and its preparation method |
| CN103773450A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method for processing inferior raw material |
| CN103773462A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Two-stage hydrocracking method used for producing high-quality chemical raw materials |
| CN104611050A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalytic cracking diesel fuel conversion method |
| CN104611029A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalytic cracking diesel fuel hydroconversion method |
| CN105295998A (en) * | 2014-07-25 | 2016-02-03 | 中国石油化工股份有限公司 | Method for producing small-molecule aromatics from diesel oil raw material |
-
2016
- 2016-04-22 CN CN201610252796.9A patent/CN107304373B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100116712A1 (en) * | 2008-11-10 | 2010-05-13 | Bart Dziabala | Combination of mild hydrotreating and hydrocracking for making low sulfur diesel and high octane naphtha |
| CN102311795A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Hydrogenation method for producing high-octane gasoline components by diesel oil raw material |
| CN102463147A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Medium oil type hydrocracking catalyst and its preparation method |
| CN103773450A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method for processing inferior raw material |
| CN103773462A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Two-stage hydrocracking method used for producing high-quality chemical raw materials |
| CN104611050A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalytic cracking diesel fuel conversion method |
| CN104611029A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalytic cracking diesel fuel hydroconversion method |
| CN105295998A (en) * | 2014-07-25 | 2016-02-03 | 中国石油化工股份有限公司 | Method for producing small-molecule aromatics from diesel oil raw material |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102428229B1 (en) | 2017-11-29 | 2022-08-01 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Modified Y-type molecular sieve and manufacturing method, hydrocracking catalyst and manufacturing method, and hydrocarbon oil hydrocracking method |
| KR20200088471A (en) * | 2017-11-29 | 2020-07-22 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Modified Y-type molecular sieve and production method, hydrolysis catalyst and production method, and hydrocarbon oil hydrolysis method |
| JP2021504281A (en) * | 2017-11-29 | 2021-02-15 | 中国石油化工股▲ふん▼有限公司 | Modified Y-type molecular sieve and production method, hydrogenation decomposition catalyst and production method, and hydrogenation decomposition method of hydrocarbon oil |
| RU2744001C1 (en) * | 2017-11-29 | 2021-03-01 | Чайна Петролиум энд Кемикал Корпорейшн | Modified y-type molecular sieve and method for producing same, hydrocracking catalyst, method for producing same and method for petroleum oil hydrocracking |
| US11179705B2 (en) | 2017-11-29 | 2021-11-23 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve and preparation method thereof, hydrocracking catalyst and preparation method thereof, and method for hydrocracking hydrocarbon oil |
| WO2019104543A1 (en) * | 2017-11-29 | 2019-06-06 | 中国石油化工股份有限公司 | Modified y-type molecular sieve and preparation method therefor, hydrocracking catalyst and preparation method therefor, and method for hydrocracking hydrocarbon oil |
| JP7169354B2 (en) | 2017-11-29 | 2022-11-10 | 中国石油化工股▲ふん▼有限公司 | Modified Y-type molecular sieve and production method, hydrocracking catalyst and production method, and hydrocracking method for hydrocarbon oil |
| US11518684B2 (en) | 2018-05-28 | 2022-12-06 | China Petroleum & Chemical Corporation | NaY molecular sieve with an aluminum-rich surface and a process of preparing same |
| RU2792150C2 (en) * | 2018-05-28 | 2023-03-17 | Чайна Петролеум Энд Кемикал Корпорейшн | NaY MOLECULAR SIEVE WITH ALUMINUM-ENRICHED SURFACE AND ITS PRODUCTION METHOD |
| CN110938467A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Hydrocracking method |
| CN110938468A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Hydrocracking process |
| CN110938468B (en) * | 2018-09-25 | 2021-10-08 | 中国石油化工股份有限公司 | Hydrocracking process |
| CN110938467B (en) * | 2018-09-25 | 2021-10-08 | 中国石油化工股份有限公司 | Hydrocracking method |
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