CN106675638A - Hydrogenation conversion process for catalytic diesel oil - Google Patents
Hydrogenation conversion process for catalytic diesel oil Download PDFInfo
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- CN106675638A CN106675638A CN201510750194.1A CN201510750194A CN106675638A CN 106675638 A CN106675638 A CN 106675638A CN 201510750194 A CN201510750194 A CN 201510750194A CN 106675638 A CN106675638 A CN 106675638A
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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
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The invention discloses a hydrogenation conversion process for catalytic diesel oil. The hydrogenation conversion process comprises the following contents: firstly, under the condition of a hydrofining process, a mixture of raw materials of the catalytic diesel oil and hydrogen first enters a pretreatment reactor for a hydrofining reaction; secondly, a hydrofining reaction effluent enters a cracking reactor, wherein the upper part of the cracking reactor is filled with a hydrocracking catalyst containing a Y molecular sieve; the lower part of the cracking reactor is filled with a hydrocracking catalyst containing a beta molecular sieve, wherein the filling volumetric ratio of the hydrocracking catalyst containing the Y molecular sieve to the hydrocracking catalyst containing the beta molecular sieve is (1 to 5) to (5 to 1), the content of metal oxides serving as active components of the hydrocracking catalyst containing the Y molecular sieve is higher than metal oxides serving as active components of the hydrocracking catalyst containing the beta molecular sieve by 2 to 10 weight percent; thirdly, a hydrocracking reaction effluent is separated and fractionated to obtain a high-octane gasoline product and a high-cetane diesel oil product. According to the process, high-octane gasoline and high-cetane clean diesel oil can be produced.
Description
Technical field
The invention belongs to hydrotreating techniques field, relates in particular to a kind of catalytic diesel oil hydroconversion process.
Background technology
Into new century since, with increasingly the strengthening of people's environmental consciousness, the fast development of the increasingly strict and national economy of national environmental protection regulation, countries in the world are all being continuously increased to the demand for cleaning automotive fuel.Catalytic cracking（FCC）Technology is one of main technique means of heavy oil lighting, and important status is all occupied in the oil refining enterprise of countries in the world.China's catalytic cracking unit annual working ability alreadys exceed at present 100,000,000 tons, is only second to the U.S..In petrol and diesel oil product are constituted, catalytically cracked gasoline accounts for 80% or so, and catalytic diesel oil accounts for 30% or so.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 product of catalytic cracking, particularly catalytic diesel oil quality is caused more to deteriorate.
To improve the utilization rate of petroleum resources, improve the total quality level of petrol and diesel oil fuel, realize product blending optimization and the maximized target of value of the product, meet the domestic hydrocracking process technology to clean fuel increasing need, high aromatics diesel hydro-conversion production high added value Petroleum 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.The meeting of nineteen ninety-five NPRA, David A.Pappal et al. describe a kind of single-stage hydrocracking Technology developed by Mobil, Akzo Nobel/Nippon Ketjen and M.W.Kellogg companies；NPRA meetings in 2005, Vasant P. Thakkar et al. describe the LCO UnicrackingTM technologies of Uop Inc.'s exploitation.The catalytic cycle oil ingredient of low value can be converted into high octane gasoline component and fine-quality diesel oil blending component by above two technology.Catalytic diesel oil hydroconversion process process technology is characterized by while realizing bicyclo- in catalytic diesel oil fraction, thrcylic aromatic hydrocarbon open loop cracking, retain the mononuclear aromatics in gasoline fraction as far as possible, the ring-opening reaction of gasoline fraction aromatic hydrocarbons is reduced, so as to reaching raising diesel oil distillate Cetane number simultaneously and retaining the high-octane double effectses of gasoline fraction.In order to reach this purpose, the raising of hydrocracking catalyst performance is it is critical only that, be especially the selection of the species of hydrocracking catalyst molecular sieve and the optimization of modifying process.US2010116712 discloses a kind of catalytic diesel oil hydrogenating conversion process, and the method first passed around and contacted with Cracking catalyst after pretreatment using common process method and Cracking catalyst, raw oil, and diesel oil and high-new alkane value gasoline are cleaned in production.But, aromatic hydrocarbons cracking rate is higher in the method gasoline component, 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 is made up of beta-molecular sieve and boehmite, using conventional method addition vib and group VIII active metal component, but the catalyst aromatic hydrocarbons open loop ability is poor, reaction conversion ratio and diesel quality are poor.Chinese patent CN96120016.2 discloses a kind of high silicon crystallinity Y type molecular sieve and preparation method thereof, with NH4NaY is reaction raw materials, ammonium hexafluorosilicate dealumination complement silicon is used first, then hydrothermal treatment consists are carried out, finally again with aluminum salt solution process, gained Y molecular sieve is while deep sealumination modified, maintain higher degree of crystallinity, but, gained modified Y molecular sieve pore volume should be relatively low, the unfavorable diffusion for generating gasoline fraction mononuclear aromatics, desorption, cause the further second pyrolysises of gasoline fraction mononuclear aromatics, cause gasoline fraction loss of octane number serious；United States Patent (USP) US4036739 discloses a kind of method for hydrogen cracking, it is disclosed that a kind of method of modifying of Y type molecular sieve, at a temperature of 315 ~ 899 DEG C, and process a period of time is contacted with least 0.5psi vapor, gained modified Y molecular sieve lattice constant is 2.440 ~ 2.464nm；Y molecular sieve after process is carried out into ammonium exchange, intermedium of the sodium content less than 1% is obtained；Then, obtain modified Y molecular sieve of the lattice constant less than 2.440nm, but, due to the processing procedure it is more harsh so that the destruction of the modified Y molecular sieve degree of crystallinity of acquisition is serious, and degree of crystallinity is relatively low, the Activity and stabill of catalyst.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of catalytic diesel oil hydroconversion process, and the technique can produce high-knock rating gasoline and high cetane number cleans the purpose of diesel oil.
A kind of catalytic diesel oil hydroconversion process of the present invention, including herein below：
（1）Under the conditions of hydrofining technology, catalytic diesel oil raw material is introduced into preatreating reactors and carries out hydrofining reaction with the mixture of hydrogen；
（2）Hydrofining reaction effluent enters cracker, the hydrocracking catalyst of the cracker top filling containing Y molecular sieve, hydrocracking catalyst of the bottom filling containing beta-molecular sieve；The described hydrocracking catalyst containing Y molecular sieve is 1 with the admission space of hydrocracking catalyst containing beta-molecular sieve ratio:5~5:1, preferably 1:3~3:1, the activity component metal oxide content ratio of the hydrocracking catalyst containing Y molecular sieve contains the high 2wt% ~ 10wt% of activity component metal oxide content of the hydrocracking catalyst of beta-molecular sieve, preferred 4wt ~ 8wt%；
（3）Hydrocracking reaction effluent obtains high octane gasoline products and high cetane number diesel product through separating with fractional distillation.
The inventive method step（1）In, described hydrofining technology condition is as follows：300 ~ 400 DEG C of reaction temperature, preferably 340 DEG C ~ 380 DEG C；Reaction pressure 4.0Mpa ~ 15.0Mpa, preferred 6.0Mpa ~ 12.0Mpa；0.5 ~ 4.0h of volume space velocity-1, preferably 1.0 ~ 3.0h-1；Hydrogen to oil volume ratio 200:1~2000:1, preferably 500:1~1500:1.Using catalyst for refining can use commercially available prod, it is also possible to according to this area Conventional wisdom prepare.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 aluminium 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 inventive method step（2）In, cracking reaction condition is as follows：Reaction temperature is 340～440 DEG C, preferably 360～430 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, preferably 0.5～3.0h-1；Hydrogen to oil volume ratio is 200:1~2000:1, preferably 500:1~1500:1.
The inventive method step（2）In, the composition and property of the hydrocracking catalyst containing Y molecular sieve is as follows：With carrier 65% ~ 90% of the overall catalyst weight gauge containing modified Y molecular sieve, the group VIII and/or vib metals 10% ~ 35% in terms of oxide；Wherein described modified Y molecular sieve mass percent in the carrier is 30% ~ 90%, preferably 40% ~ 80%, balance of amorphous silica-alumina and/or aluminium oxide, described modified Y molecular sieve, 500 ~ 800m of specific surface area2/ g, 0.2 ~ 0.7ml/g of pore volume, wherein the secondary pore volume accounting more than 40% of 2 ~ 7nm, generally 50 ~ 60%, meleic acid 0.6 ~ 1.5mmol/g of amount, Na2O mass contents are less than 0.15%, SiO2/Al2O3Mol ratio 7 ~ 30, lattice constant 2.435 ~ 2.450, the product of secondary pore ratio is 0.4-0.6 between degree of crystallinity and 2 ~ 7nm.The group VIII metal can be Ni and/or Co, and vib active metal can be W and/or Mo, and in terms of metal-oxide, group VIII tenor is 3% ~ 15%, and vib metals content is 10% ~ 30%.
The inventive method step（2）In, the hydrocracking catalyst containing beta-molecular sieve can be prepared using commercial catalyst or according to prior art.The composition of catalyst is as follows：Carrier 70% ~ 95% containing modified beta molecular sieve, the group VIII and/or vib metals 5% ~ 30% in terms of oxide；Wherein described modified beta molecular sieve mass percent in the carrier is 20% ~ 70%, preferably 30% ~ 50%, balance of amorphous silica-alumina and/or aluminium oxide, described modified beta molecular sieve, 300 ~ 700m of specific surface area2/ g, 0.2 ~ 0.60ml/g of pore volume, infrared 0.1 ~ 0.5mmol/g of acid content.The group VIII metal can be Ni and/or Co, and vib active metal can be W and/or Mo, and in terms of metal-oxide, group VIII tenor 2% ~ 12%, vib metals content is 8% ~ 25%.
The inventive method step（2）In, the hydrocracking catalyst containing Y molecular sieve is adopted and prepared with the following method：By modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide mix homogeneously, add dust technology into extruded moulding after slurry, drying, roasting obtain the carrier containing modified Y molecular sieve；Carrier is impregnated using the impregnation liquid containing group VIII and/or vib metals, the carrier drying after dipping, roasting obtain hydrocracking catalyst；The preparation of wherein modified Y molecular sieve comprises the steps：
（1）Ammonium Salt Ionic is carried out in ammonium salt solution as former powder with NaY zeolite to exchange to Na2O weight contents are less than 2.0%；
（2）To step（1）In the ammonium that obtains exchange after Y molecular sieve carry out hydrothermal treatment consists；
（3）Step（2）The hydrothermal treatment consists Y molecular sieve for obtaining carries out sodium ion exchange in sodium salt solution；
（4）By step（3）The Y molecular sieve for obtaining is carried out after ammonium fluosilicate dealumination complement silicon process, and Jing after filtration, dry, roasting final Modified Zeolite Y is obtained.
In said method, the concentration of the dust technology added during extruded moulding is 3wt% ~ 30wt%；Drying condition is after molding：It is dried 1 ~ 5 hour at 80 ~ 120 DEG C；Roasting condition is：Roasting 1 ~ 5 hour at 400 ~ 700 DEG C.
In said method, the liquid-solid ratio that the impregnation liquid containing group VIII and/or vib metals impregnates when impregnating to carrier is 1.5：1~3：1.Carried out by the way of saturation well known in the art dipping, the content of group vib metallic compound is calculated as 20 ~ 60g/100ml by corresponding oxide in impregnation liquid, the content of group VIII metallic compound is calculated as 3 ~ 20g/100ml by corresponding oxide, and the concentration of metallic compound can be adjusted accordingly according to product needed in impregnation liquid.Described drying condition is after dipping：It is dried 2 ~ 8 hours at 90 ~ 150 DEG C；Roasting condition is：Roasting 1 ~ 5 hour at 400 ~ 700 DEG C.
In said method, step（1）Described in Ammonium Salt Ionic exchange process it is as follows：It is raw material in ammonium salt aqueous solution with NaY zeolite, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, exchange times is 1 ~ 2 time, the NaY zeolite after being exchanged, Na2O mass contents are less than 1.5%；Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, sodium oxide weight/mass percentage composition 6% ~ 7%；Ammonium salt is one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0 ~ 3.0 mol/L.
In said method, step（2）The hydrothermal treatment process is that hydrothermal conditions are in itself vapor or under conditions of being passed through vapor：Temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.2MPa, and process time is 1.0 ~ 4.0 hours.
In said method, step（3）Described in sodium salt ion exchange process it is as follows：With step（2）Y molecular sieve after middle hydrothermal treatment consists is put in sodium-salt aqueous solution for raw material, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, is exchanged 1 ~ 3 hour, and exchange times are 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O mass contents are not less than 3.0%；Sodium salt is one or more in Sodium Chloride, sodium nitrate, sodium sulfate, sodium citrate, Disodium oxalate., sodium-salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0 ~ 3.0 mol/L.It is preferred that adding the removing of the non-framework aluminum that glycerol promotion hydrothermal treatment process is generated in sodium salt solution and improving sodium salt exchange efficiency, glycerol concentration is 0.1 ~ 2.0 in sodium salt solution, preferred 0.1-0.5 mol/L.
In said method, step（4）Described in dealumination complement silicon be processed as method well known to those skilled in the art, can be using conventional ammonium fluosilicate dealumination complement silicon method, by step（3）The Y molecular sieve for obtaining is according to the solid mass ratio 3 of liquid：1~20：1, preferably 5:1~10:1 with ammonium fluosilicate aqueous solution, wherein in ammonium fluosilicate solution ammonium fluosilicate concentration be 0.01 ~ 0.8mol/L, preferably 0.1 ~ 0.6 mol/L, in 50 ~ 100 DEG C process 0.5 ~ 6 hour.
In said method, step（4）In ammonium fluosilicate dealumination complement silicon during, the mineral acids such as nitric acid, hydrochloric acid, acetic acid, citric acid, oxalic acid or organic acid can be added in ammonium fluosilicate solution preferably to remove the concentration of the non-framework aluminum in molecular sieve, mineral acid and/or organic acid with H+It is calculated as 0.1 ~ 0.6mol/L, preferably 0.1 ~ 0.4mol/L.
Research finds, from top to bottom with the intensification of reaction depth in catalytic diesel oil hydroconversion unit cracker, gasoline fraction ratio is gradually stepped up in reactant fraction, diesel oil distillate ratio is gradually reduced, according to this reaction characteristics, using two kinds of different filling hydrocracking catalyst at different stages in hydrocracking reactor in the inventive method, its middle and upper part filling is conducive to bicyclo- and thrcylic aromatic hydrocarbon ring-opening reaction in diesel oil distillate to carry out containing Y molecular sieve, the hydrocracking catalyst of high activity metal content, improves diesel product Cetane number；Bottom bed filling reduces the gasoline fraction mononuclear aromatics open loop ability of course of reaction production containing beta-molecular sieve, the hydrocracking catalyst of low activity tenor, be conducive to retaining more mononuclear aromatics, gasoline fraction octane number is improved, while having reached the purpose for improving diesel oil and gasoline product quality.Additionally, present invention preferably employs modified molecular screen first by exchanging molecular screen primary powder ammonia to reduce molecular sieve Na contents, improve hydrothermal treatment consists efficiency, and reduce hydrothermal treatment process skeleton destructiveness.By supplementing Na ions, promote the dealumination complement silicon reaction of follow-up ammonium fluosilicate processing procedure is carried out molecular sieve after hydrothermal treatment consists.Therefore, process of the present invention improves the reaction efficiency of hydrothermal treatment consists and ammonium fluosilicate simultaneously, and modified molecular screen remains the secondary pore volume of hydrothermal treatment process greatly and ammonium fluosilicate processing procedure is the characteristics of deep sealumination modified and high skeleton crystal degree.
Specific embodiment
Next step further describes the technical characterstic of the present invention by embodiment, but these embodiments can not limit the present invention.% in following examples is such as weight/mass percentage composition without special marking.
Embodiment 1
（1）NaY molecular sieve original powder 200g is taken, with the ammonium nitrate that concentration is 2.3mol/L according to liquid-solid ratio 4:1 mixing, 70 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 1.7%；
（2）To step（1）540 DEG C of the Y molecular sieve for obtaining, hydrothermal treatment consists 2 hours under 0.2Mpa；
（3）To step（2）The Y molecular sieve concentration for obtaining is the sodium chloride solution of 1.7mol/L according to liquid-solid ratio 5:1 mixing, 65 DEG C exchange 1 hour, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 3.8%；
（4）Step（3）The molecular sieve of gained is according to liquid-solid ratio 5:1 and 0.3mol/L ammonium fluosilicate and 0.2mol/L citric acids（In terms of H+）Solution mixing beating, 85 DEG C process 2 hours；
（5）Jing steps（4）Y molecular sieve after process, 120 DEG C of dryings 2 hours obtain the molecular sieve of embodiment 1, and numbering is Y-1.
The preparation of the hydrocracking catalyst containing Y molecular sieve：
（1）Configuration W-Ni dipping solutions：Take ammonium metatungstate and configure dipping solution after nickel nitrate is dissolved in water, active metal is with WO in gained dipping solution336g/100ml and 10g/100ml, solution numbers RY-1 are respectively with NiO cubages；
（2）Take Y-1 60g to mix with 40g macroporous aluminium oxides, add 4g/100ml dust technologies to mix in a mixer and roll to extrudable shape, extruded moulding obtains carrier T-1 on banded extruder；
（3）Taking T-1 60g adds 120ml RY-1 impregnation liquid to impregnate 2 hours, then 120 DEG C of dryings 4 hours, 500 DEG C of roastings 3 hours, obtains hydrocracking catalyst, and numbering is C-1.
Embodiment 2
（1）NaY molecular sieve original powder 200g is taken, with the ammonium chloride that concentration is 2.5mol/L according to liquid-solid ratio 5:1 mixing, 85 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 1.2%；
（2）To step（1）530 DEG C of the Y molecular sieve for obtaining, hydrothermal treatment consists 1.5 hours under 0.10Mpa；
（3）To step（2）The Y molecular sieve concentration for obtaining is the sodium nitrate of 1.2mol/L according to liquid-solid ratio 5:1 mixing, 80 DEG C exchange 1 hour, repeat this process 2 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 3.5%；
（4）Step（3）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes beating with concentration for the ammonium fluosilicate solution of 0.3mol/L, and 95 DEG C are processed 2 hours；
（5）Jing steps（4）Y molecular sieve after ammonium fluosilicate process, 120 DEG C of dryings 2 hours obtain the molecular sieve of embodiment 1, and numbering is Y-2.
The preparation of the hydrocracking catalyst containing Y molecular sieve：
（1）Configuration W-Ni dipping solutions：Take ammonium metatungstate and configure dipping solution after nickel nitrate is dissolved in water, active metal is with WO in gained dipping solution336g/100ml and 10g/100ml, solution numbers RY-2 are respectively with NiO cubages；
（2）Take Y-2 50g to mix with 50g macroporous aluminium oxides, add 4g/100ml dust technologies to mix in a mixer and roll to extrudable shape, extruded moulding obtains carrier T-2 on banded extruder；
（3）Taking T-2 60g adds 120ml RY-2 impregnation liquid to impregnate 2 hours, then 120 DEG C of dryings 4 hours, 500 DEG C of roastings 3 hours, obtains hydrocracking catalyst, and numbering is C-2.
Embodiment 3
（1）NaY molecular sieve original powder 200g is taken, with the ammonium nitrate that concentration is 1.7mol/L according to liquid-solid ratio 3:1 mixing, 90 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 1.8%；
（2）To step（1）580 DEG C of the Y molecular sieve for obtaining, hydrothermal treatment consists 2 hours under 0.15Mpa；
（3）To step（2）The Y molecular sieve for obtaining is respectively the mixed solution of 2.5mol/L and 0.25mol/L according to liquid-solid ratio 5 with containing sodium nitrate and glycerol:1 mixing, 80 DEG C exchange 1 hour, repeat this process 2 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 5.5%；
（4）Step（3）The molecular sieve of gained is according to liquid-solid ratio 10:1 mixes beating with concentration for the ammonium fluosilicate solution of 0.4mol/L, and 90 DEG C are processed 2 hours；
（5）Jing steps（4）Y molecular sieve after ammonium fluosilicate process, 120 DEG C of dryings 2 hours obtain the molecular sieve of embodiment 1, and numbering is Y-3.
The preparation of the hydrocracking catalyst containing Y molecular sieve：
（1）Configuration W-Ni dipping solutions：Take ammonium metatungstate and configure dipping solution after nickel nitrate is dissolved in water, active metal is with WO in gained dipping solution336g/100ml and 10g/100ml, solution numbers RY-3 are respectively with NiO cubages；
（2）Take Y-3 70g to mix with 30g macroporous aluminium oxides, add 4g/100ml dust technologies to mix in a mixer and roll to extrudable shape, extruded moulding obtains carrier T-3 on banded extruder；
（3）Taking T-3 60g adds 120ml RY-3 impregnation liquid to impregnate 2 hours, then 120 DEG C of dryings 4 hours, 500 DEG C of roastings 3 hours, obtains hydrocracking catalyst, and numbering is C-3.
The physicochemical property of the modified Y molecular sieve of embodiment 1 ~ 3 is listed in the table below 1.
The embodiment molecular sieve physico-chemical property of table 1
Embodiment
5
Catalytic diesel oil raw material（Property is shown in Table 2）Being introduced into preatreating reactors with the mixture of hydrogen carries out hydrofining reaction, and reaction condition is as follows：360 DEG C of reaction temperature, reaction pressure 8.0Mpa, volume space velocity 1.5h-1, hydrogen to oil volume ratio 1200, Hydrobon catalyst is consisted of： WO3 20wt% 、NiO 6wt %、Al2O3
74wt% .Hydrofining reaction effluent enters cracker, hydrocracking catalyst containing Y molecular sieve, the hydrocracking catalyst containing beta-molecular sieve of bottom filling routine prepared by the cracker top filling embodiment 1, consist of with overall catalyst weight gauge WO315wt%, NiO 3wt %, the wt % Al of beta-molecular sieve 252O3
57wt% ；Admission space ratio is 2:1 ；The activity component metal oxide content ratio of the hydrocracking catalyst containing Y molecular sieve contains the high 4wt% of activity component metal oxide content of the hydrocracking catalyst of beta-molecular sieve, and reaction condition is as follows：398 DEG C of reaction temperature, reaction pressure 8.0Mpa, volume space velocity 1.5h-1, hydrogen to oil volume ratio 1200.Hydrocracking reaction effluent obtains gasoline products through separation and fractional distillation and diesel product property is shown in Table 3.
Embodiment
6
Catalytic diesel oil raw material（Property is shown in Table 2）Being introduced into preatreating reactors with the mixture of hydrogen carries out hydrofining reaction, and reaction condition is as follows：360 DEG C of reaction temperature, reaction pressure 8.0Mpa, volume space velocity 1.5h-1, hydrogen to oil volume ratio 1200, Hydrobon catalyst is consisted of： WO3 20wt% 、NiO 6wt %、Al2O3
74wt%.Hydrofining reaction effluent enters cracker, the hydrocracking catalyst containing Y molecular sieve, the hydrocracking catalyst containing beta-molecular sieve of bottom filling routine prepared by the cracker top filling embodiment 2, consists of WO313wt%, NiO 2wt %, beta-molecular sieve 25wt% Al2O3
60wt%；Admission space ratio is 1:2；The activity component metal oxide content ratio of the hydrocracking catalyst containing Y molecular sieve contains the high 8wt% of activity component metal oxide content of the hydrocracking catalyst of beta-molecular sieve, and reaction condition is as follows：408 DEG C of reaction temperature, reaction pressure 8.0Mpa, volume space velocity 1.5h-1, hydrogen to oil volume ratio 1200.Hydrocracking reaction effluent obtains gasoline products through separation and fractional distillation and diesel product property is shown in Table 3.
Embodiment
7
Catalytic diesel oil raw material（Property is shown in Table 2）Being introduced into preatreating reactors with the mixture of hydrogen carries out hydrofining reaction, and reaction condition is as follows：360 DEG C of reaction temperature, reaction pressure 8.0Mpa, volume space velocity 1.5h-1, hydrogen to oil volume ratio 1200, Hydrobon catalyst is consisted of： WO3 20wt% 、NiO 6wt %、Al2O3
74wt%.Hydrofining reaction effluent enters cracker, the hydrocracking catalyst containing Y molecular sieve, the hydrocracking catalyst containing beta-molecular sieve of bottom filling routine prepared by the cracker top filling embodiment 3, consists of WO313wt%, NiO 2wt %, beta-molecular sieve 25wt% Al2O3
60wt%；Admission space ratio is 1:1 ；The activity component metal oxide content ratio of the hydrocracking catalyst containing Y molecular sieve contains the high 8wt% of activity component metal oxide content of the hydrocracking catalyst of beta-molecular sieve;Reaction condition is as follows：401 DEG C of reaction temperature, reaction pressure 8.0Mpa, volume space velocity 1.5h-1, hydrogen to oil volume ratio 1200.Hydrocracking reaction effluent obtains gasoline products through separation and fractional distillation and diesel product property is shown in Table 3.
Embodiment 8
With embodiment 1, difference is the conventional hydrocracking catalyst containing Y molecular sieve prepared by the cracker top filling prior art, consists of WO316wt%, NiO 6wt %, Y molecular sieve 45wt%, Al2O3
33wt%.Hydrocracking reaction effluent obtains gasoline products through separation and fractional distillation and diesel product property is shown in Table 3.
Comparative example 1
The conventional hydrocracking catalyst containing Y molecular sieve is all loaded in cracker, the hydrocracking catalyst containing beta-molecular sieve is not loaded.Hydrocracking reaction effluent obtains gasoline products through separation and fractional distillation and diesel product property is shown in Table 3.
The raw material oil nature of table 2.
| Raw oil | Catalytic diesel oil |
| Density, g/cm3 | 0.9324 |
| Boiling range, DEG C | 192～350 |
| S, m% | 1.54 |
| N, % | 800 |
| Aromatic hydrocarbons | 72 |
| Cetane number | 18 |
Table 3
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 | |
| Conversion per pass, m% | 58 | 58 | 58 | 58 | 58 |
| Chemical hydrogen consumption, m% | 3.32 | 3.25 | 3.18 | 3.44 | 3.65 |
| Product slates, m% | |||||
| Naphtha cut fraction（210 DEG C of ＜） | 53 | 54 | 56 | 50 | 46 |
| Diesel oil distillate（210 DEG C of ＞） | 42 | 42 | 42 | 42 | 42 |
| Product property | |||||
| Petroleum（210 DEG C of ＜） | |||||
| Octane number | 94 | 95 | 98 | 90 | 85 |
| Diesel oil（210 DEG C of ＞） | |||||
| Cetane number | 33 | 30 | 36 | 30 | 26 |
Claims (21)
1. a kind of catalytic diesel oil hydroconversion process, it is characterised in that：Including herein below：
（1）Under the conditions of hydrofining technology, catalytic diesel oil raw material is introduced into preatreating reactors and carries out hydrofining reaction with the mixture of hydrogen；
（2）Hydrofining reaction effluent enters cracker, the hydrocracking catalyst of the cracker top filling containing Y molecular sieve, hydrocracking catalyst of the bottom filling containing beta-molecular sieve；The described hydrocracking catalyst containing Y molecular sieve is 1 with the admission space of hydrocracking catalyst containing beta-molecular sieve ratio:5~5:1, the activity component metal oxide content ratio of the hydrocracking catalyst containing Y molecular sieve contains the high 2wt% ~ 10wt% of activity component metal oxide content of the hydrocracking catalyst of beta-molecular sieve；
（3）Hydrocracking reaction effluent obtains gasoline products and diesel product through separating with fractional distillation.
2. method according to claim 1, it is characterised in that：Step（1）Middle hydrofining technology condition is as follows：300 ~ 400 DEG C of reaction temperature；Reaction pressure 4.0Mpa ~ 15.0Mpa；0.5 ~ 4.0h of volume space velocity-1；Hydrogen to oil volume ratio 200:1~2000:1.
3. method according to claim 2, it is characterised in that：Hydrofining technology condition is as follows：340 DEG C ~ 380 DEG C of reaction temperature；Reaction pressure 6.0Mpa ~ 12.0Mpa；1.0 ~ 3.0h of volume space velocity-1；Hydrogen to oil volume ratio 500:1~1500:1.
4. method according to claim 1, it is characterised in that：Step（1）The middle Hydrobon catalyst for adopting with group vib and/or group VIII metal as active component, with aluminium oxide or silicon-containing alumina as carrier.
5. method according to claim 4, it is characterised in that：Vib metals are Mo and/or W, and group VIII metal is Co and/or Ni, and 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.
6. method according to claim 1, it is characterised in that：Step（2）Middle cracking reaction condition is as follows：Reaction temperature is 340～440 DEG C；Reaction pressure is 4.0～15.0MPa；Volume space velocity is 0.2～6.0h during liquid-1；Hydrogen to oil volume ratio is 200:1~2000:1.
7. method according to claim 6, it is characterised in that：Cracking reaction condition is as follows：Reaction temperature is 360～430 DEG C；Reaction pressure is 6.0～12.0MPa；Volume space velocity is 0.5～3.0h during liquid-1；Hydrogen to oil volume ratio is 500:1~1500:1.
8. method according to claim 1, it is characterised in that：Step（2）Described in the hydrocracking catalyst containing Y molecular sieve and the admission space of hydrocracking catalyst containing beta-molecular sieve ratio be 1:3~3:1, the activity component metal oxide content ratio of the hydrocracking catalyst containing Y molecular sieve contains the high 4wt ~ 8wt% of activity component metal oxide content of the hydrocracking catalyst of beta-molecular sieve.
9. method according to claim 1, it is characterised in that：Step（2）In the hydrocracking catalyst containing Y molecular sieve composition and property it is as follows：With carrier 65% ~ 90% of the overall catalyst weight gauge containing modified Y molecular sieve, the group VIII and/or vib metals 10% ~ 35% in terms of oxide；Wherein described modified Y molecular sieve mass percent in the carrier is 30% ~ 90%, balance of amorphous silica-alumina and/or aluminium oxide.
10. method according to claim 9, it is characterised in that：Described modified Y molecular sieve, 500 ~ 800m of specific surface area2/ g, 0.2 ~ 0.7ml/g of pore volume, wherein the secondary pore volume accounting more than 40% of 2 ~ 7nm, meleic acid 0.6 ~ 1.5mmol/g of amount, Na2O mass contents are less than 0.15%, SiO2/Al2O3Mol ratio 7 ~ 30, lattice constant 2.435 ~ 2.450, the product of secondary pore ratio is 0.4-0.6 between degree of crystallinity and 2 ~ 7nm.
11. methods according to claim 9, it is characterised in that：The group VIII metal is Ni and/or Co, and vib active metal is W and/or Mo, and in terms of metal-oxide, group VIII tenor is 3% ~ 15%, and vib metals content is 10% ~ 30%.
12. methods according to claim 1, it is characterised in that：Step（2）In containing beta-molecular sieve hydrocracking catalyst composition it is as follows：Carrier 70% ~ 95% containing modified beta molecular sieve, the group VIII and/or vib metals 5% ~ 30% in terms of oxide；Wherein described modified beta molecular sieve mass percent in the carrier is 20% ~ 70%, balance of amorphous silica-alumina and/or aluminium oxide, described modified beta molecular sieve, 300 ~ 700m of specific surface area2/ g, 0.2 ~ 0.60ml/g of pore volume, infrared 0.1 ~ 0.5mmol/g of acid content, the group VIII metal is Ni and/or Co, and vib active metal is W and/or Mo, and in terms of metal-oxide, group VIII tenor 2% ~ 12%, vib metals content is 8% ~ 25%.
13. methods according to claim 1, it is characterised in that：Step（2）In the hydrocracking catalyst containing Y molecular sieve adopt and prepare with the following method：By modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide mix homogeneously, add dust technology into extruded moulding after slurry, drying, roasting obtain the carrier containing modified Y molecular sieve；Carrier is impregnated using the impregnation liquid containing group VIII and/or vib metals, the carrier drying after dipping, roasting obtain hydrocracking catalyst；The preparation of wherein modified Y molecular sieve comprises the steps：
（1）Ammonium Salt Ionic is carried out in ammonium salt solution as former powder with NaY zeolite to exchange to Na2O weight contents are less than 2.0%；
（2）To step（1）In the ammonium that obtains exchange after Y molecular sieve carry out hydrothermal treatment consists；
（3）Step（2）The hydrothermal treatment consists Y molecular sieve for obtaining carries out sodium ion exchange in sodium salt solution；
（4）By step（3）The Y molecular sieve for obtaining is carried out after ammonium fluosilicate dealumination complement silicon process, and Jing is filtered, is dried, roasting obtains final Modified Zeolite Y.
14. methods according to claim 13, it is characterised in that：The concentration of the dust technology added during extruded moulding is 3wt% ~ 30wt%；Drying condition is after molding：It is dried 1 ~ 5 hour at 80 ~ 120 DEG C；Roasting condition is：Roasting 1 ~ 5 hour at 400 ~ 700 DEG C.
15. methods according to claim 13, it is characterised in that：The liquid-solid ratio that impregnation liquid containing group VIII and/or vib metals impregnates when impregnating to carrier is 1.5：1~3：1, by the way of saturation dipping, the content of group vib metallic compound is calculated as 20 ~ 60g/100ml by corresponding oxide in impregnation liquid, and the content of group VIII metallic compound is calculated as 3 ~ 20g/100ml by corresponding oxide, and drying condition is after dipping：It is dried 2 ~ 8 hours at 90 ~ 150 DEG C；Roasting condition is：Roasting 1 ~ 5 hour at 400 ~ 700 DEG C.
16. methods according to claim 13, it is characterised in that：Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：It is raw material in ammonium salt aqueous solution with NaY zeolite, at 60 ~ 120 DEG C, exchanges 1 ~ 3 hour, exchange times is 1 ~ 2 time, the NaY zeolite after being exchanged, Na2O mass contents are less than 1.5%；Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, sodium oxide weight/mass percentage composition 6% ~ 7%；Ammonium salt is one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution 0.3 ~ 6.0mol/L of concentration.
17. methods according to claim 13, it is characterised in that：Step（2）The hydrothermal treatment process is that hydrothermal conditions are in itself vapor or under conditions of being passed through vapor：Temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.2MPa, and process time is 1.0 ~ 4.0 hours.
18. methods according to claim 13, it is characterised in that：Step（3）Described in sodium salt ion exchange process it is as follows：With step（2）Y molecular sieve after middle hydrothermal treatment consists is put in sodium-salt aqueous solution for raw material, at 60 ~ 120 DEG C, is exchanged 1 ~ 3 hour, and exchange times are 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O mass contents are not less than 3.0%；Sodium salt is one or more in Sodium Chloride, sodium nitrate, sodium sulfate, sodium citrate, Disodium oxalate., sodium-salt aqueous solution 0.3 ~ 6.0mol/L of concentration.
19. methods according to claim 18, it is characterised in that：Add glycerol in sodium salt solution, glycerol concentration is 0.1 ~ 2.0 in sodium salt solution
mol/L。
20. methods according to claim 13, it is characterised in that：Step（4）Described in dealumination complement silicon process adopt ammonium fluosilicate dealumination complement silicon method, by step（3）The Y molecular sieve for obtaining is according to the solid mass ratio 3 of liquid：1~20：1 with ammonium fluosilicate aqueous solution, wherein in ammonium fluosilicate solution ammonium fluosilicate concentration be 0.01 ~ 0.8mol/L, in 50 ~ 100 DEG C process 0.5 ~ 6 hour.
21. methods according to claim 20, it is characterised in that：Step（4）In ammonium fluosilicate dealumination complement silicon during, the concentration of mineral acid or organic acid, mineral acid and/or organic acid is added in ammonium fluosilicate solution with H+It is calculated as 0.1 ~ 0.6mol/L.
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| CN112742459A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrocracking catalyst, preparation method and application thereof |
| CN112745921A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Hydroconversion process for long side chain alkyl containing aromatic hydrocarbon feed |
| CN115646540A (en) * | 2022-10-24 | 2023-01-31 | 山东公泉化工股份有限公司 | Composite hydrocracking catalyst, preparation method thereof and preparation method of transformer oil |
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