CN101003746A - Combined hydrocracking method - Google Patents
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- CN101003746A CN101003746A CN 200610008413 CN200610008413A CN101003746A CN 101003746 A CN101003746 A CN 101003746A CN 200610008413 CN200610008413 CN 200610008413 CN 200610008413 A CN200610008413 A CN 200610008413A CN 101003746 A CN101003746 A CN 101003746A
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Abstract
This invention relates to a hydrogenation cracking method. The method comprises: hydrogenating inferior catalytically cracked diesel oil, mixing the hydrogenation products with VGO and other raw materials, introducing into a second hydrogenation cracking zone, and separating to obtain light products and hydrogenation tail oil. The inferior catalytically cracked diesel oil is obtained by hydrogenation-transfer catalytic cracking of heavy oil and residual oil, and has such characteristics of high density, high polycyclic aromatic hydrocarbon content, and low hexadecane number. The method combines inferior catalytically cracked diesel oil and VGO, and can produce large quantities of high-quality heavy naphtha with high content of aromatic hydrocarbon, and tail oil with low MCI value.
Description
Technical field
The present invention relates to a kind of combined hydrocracking method, particularly relate to a kind of combined hydrocracking method that can effectively handle poor quality catalytic cracking diesel.
Background technology
Along with crude oil heaviness, poor qualityization day by day, and to the minimizing of market to the heavy oil demand, to the increase of light oil demand, the degree of depth transforming degree of heavy residual oil improves constantly.Wherein catalytic cracking is one of important means of heavy residual oil lighting.But the product characteristics that catalytic cracking obtains is generally relatively poor, generally needs just can obtain qualified product through further processing again.In general the diesel oil distillate that catalytic cracking obtains has the aromaticity content height, and cetane value is low, and characteristics such as sulphur, nitrogen content height are difficult to directly as product, and common processing means also is difficult to effectively improve its quality product.
The common method of processing poor quality catalytic cracking diesel is hydrofining at present, and this technology investment is low, technology maturation, but the improvement of diesel oil is had certain restriction, generally diesel-fuel cetane number can only be improved 3-5 unit.As US 6,129, the hydrofining technology of the 835 employing routines of introducing, though impurity such as energy effective elimination sulphur, nitrogen obviously improve the color and the stability of diesel product, and keep very high diesel yield, diesel product cetane value amplification is limited.If adopt severe condition hydrofining, because hydrofining does not change the molecular structure of petroleum fractions substantially, cetane value can not be greatly improved, and because hydrogen consumption huge (more than the 4wt%), tooling cost significantly increases.
US5114562 and US5068025 etc. adopt two-stage method diesel oil hydrogenation treatment process, one section adopts traditional Hydrobon catalyst with impurity removals such as the sulphur in the raw material, nitrogen, and the hydrogenation catalyst that second section use has high hydrogenation saturated activity carries out deeply de-aromatizing.Though this technology can be taken off the aromatic hydrocarbons in the diesel oil very low degree, the hydrogen consumption is big, and investment is high, and is less economical, and cetane value improves not obvious, can not obtain qualified diesel product.
Middle pressure hydrocracking or MHUG (as patent US4971680, CN1171430A etc.) utilize hydrocracking catalyst catalytic cracking diesel oil to be carried out the processing of certain transformation efficiency, this method can improve the cetane value of catalytic cracking diesel oil ten more than the unit, and obtain the gasoline products of certain yield, but, still can not obtain qualified diesel product for the very low poor quality catalytic cracking diesel of raw material cetane value.
It is to select shape cracked technological process under hydrogen and the middle pressure condition facing that CN 1061679C has introduced the hydrodewaxing technology.It utilizes the pore passage structure of particular molecule sieve catalyst uniqueness and suitable acid sites, and the contour condensation point component of the normal paraffin in the diesel feed is carried out selective splitting, and to reduce the zero pour of diesel product, the while by-product is gasoline and C partly
3, C
4Lighter hydrocarbons.CN1257107A has introduced hydrogenation pour point depression technology.This technology adopts hydrofining-hydrodewaxing combination process flow process, by the hydrogenation pre-refining is carried out in charging, not only improved hydrodewaxing section feeding quality, improved adaptability to stock oil, prolonged the running period of device, and alleviated operational condition greatly, and the purpose quality product is greatly improved.Adopt the above-mentioned technology can the higher diesel oil distillate raw material of pour point depression wax content, can not be used to process the high poor quality catalytic cracking diesel of aromaticity content.
US5,030,780 uses the catalyst treatment diesel oil that contains Y zeolite and amorphous silicon aluminium, mainly carry out saturated to the aromatic hydrocarbons in the diesel oil, but it is limited that cetane value improves, and for the extremely low poor quality catalytic cracking diesel raw material of cetane value, still can not obtain qualified product.CN1156752A discloses a kind of diesel modifying technology, use hydrocracking catalyst, under the condition of a certain amount of nitrogen of control, make the aromatic hydrocarbons in the diesel oil carry out ring-opening reaction, can obviously improve diesel-fuel cetane number, generally cetane value can be improved 10 more than the unit.But when being used for the extremely low poor quality catalytic cracking diesel of cetane value, still can not obtain qualified product.US5,011,593 introduces a kind of sweetening process that is used for sulphur and the higher raw material of aromatic hydrocarbons amount, uses the catalyzer contain the β zeolite, and using the sulphur content of raw material is 0.5～5.0wt%, more than the aromaticity content 50wt%, as the light cycle oil of catalytic cracking etc.This patent is equivalent to adopt and contains beta-zeolite catalyst the catalytic cracking light cycle oil is carried out mild hydrocracking, for the extremely low poor quality catalytic cracking diesel of cetane value, can not obtain qualified product.
US4789457, US4919789 carry out catalytic cracking with heavy feed stock, are raw material with the catalytic cracking light cycle oil, adopt middle pressure hydrocracking to produce gasoline.US4426276 carries out catalytic cracking with the crude oil heavy ends to be handled, and catalytic cracking light cycle oil and heavy cycle oil mix with straight run intermediate oil (straight-run diesel oil) and carries out hydrocracking, and purpose is a production gasoline.The main deficiency of these technology is that the raw material of hydrocracking only is catalytic cracking turning oil, do not give full play to the upgrading function to poor quality, heavy feed stock of hydrocracking, heavy feed stock all carries out catalytic cracking to be handled, must there be more unavailable slurry oil to efflux, can not makes full use of petroleum resources.
Along with the development of catalytic cracking technology, as the catalytic hydrogen transfer technology, reduce the olefin(e) centent in the catalytically cracked gasoline, improved the hydrogen richness of catalytically cracked gasoline, improved the quality product of catalytically cracked gasoline, as described in CN1310223A etc.But catalytic cracking process does not have external hydrogen make-up, the reason that hydrogen richness in the catalytically cracked gasoline increases is by the catalytic hydrogen transfer technology, hydrogen transference in other cut has been arrived in the gasoline fraction, the hydrogen richness of other cut product is reduced greatly, hydrogen/carbon ratio is seriously lacked of proper care, and molecular structure more trends towards the lower polycyclic aromatic hydrocarbons structure of hydrogen/carbon ratio.For example the diesel oil distillate that obtains of catalytic hydrogen transfer technology is poorer than common catalytic cracking diesel oil quality, and the character that shows is that density raises, generally can reach more than the 0.9g/ml, aromaticity content increases, and generally can reach more than the 60wt%, cetane value reduces, and is generally about 20.This class poor quality catalytic cracking diesel adopts above-mentioned method of hydrotreating generally to be difficult to effective processing, and because course of processing hydrogen consumption is too big, and do not have reasonableness economically.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of combined hydrocracking processing method that can effectively handle poor quality catalytic cracking diesel, the inventive method combines poor quality catalytic cracking diesel and two kinds of materials of vacuum distillate, adopt suitable technical process, fully effectively handle and utilize poor quality catalytic cracking diesel and heavy hydrogenated cracking stock (as vacuum distillate VGO etc.) are comprehensive.
Method for hydrogen cracking of the present invention can be produced the heavy naphtha of high arene underwater content (being called for short virtue dives), specifically comprises following process:
(1) under hydroprocessing condition, with poor quality catalytic cracking diesel by containing the bed of hydrotreating catalyst;
(2) reaction effluent that obtains of step (1) and the mixture of heavy hydrogenated cracking stock, under hydrocracking condition by containing the bed of hydrotreating catalyst and hydrocracking catalyst;
(3) reaction product that obtains of step (2) is separated, and obtains various product light-end productss and hydrogenation tail oil.
Poor quality catalytic cracking diesel described in the step of the present invention (1) is a catalytic cracking diesel oil heavy, that residual oil catalytic cracking obtains, the catalytic cracking diesel oil that particularly adopts the catalytic cracking of hydrogen transference technology to obtain.Its quality characteristic is the density height, the aromaticity content height, and cetane value is low.20 ℃ of density can reach more than the 0.90g/ml, are generally 0.90～0.99g/ml, are generally 0.92～0.97g/ml; Aromaticity content can reach more than the 60wt%, is generally 6wt%～97wt%, is generally 70wt%～90wt%; Cetane value is about 20, is generally 10～30, is generally 12～25.
The described hydrotreating catalyst of step (1) is conventional hydrotreating catalyst.Hydroprocessing condition in the step (1) is conventional hydroprocessing condition, is 3～20MPa as the hydrogen dividing potential drop, preferred 5～17MPa, and temperature of reaction is 300～480 ℃, preferred 330～440 ℃, volume space velocity is 0.1～8h during liquid
-1Preferred 0.5～3h
-1, hydrogen to oil volume ratio is 100～5000, is preferably 500～2000.
Described hydrocracking catalyst of step (2) and hydrotreating catalyst are this area conventional catalyst.Reaction mass contacts with hydrotreating catalyst earlier, contacts with hydrocracking catalyst then, and the volume ratio of hydrotreating catalyst and hydrocracking catalyst is 5: 1～1: 5.Hydrocracking condition can be selected conventional operational condition, is 3～20MPa as the hydrogen dividing potential drop, preferred 5～17MPa, and temperature of reaction is 330～450 ℃, preferred 350～420 ℃, volume space velocity is 0.2～8h during total liquid
-1, preferred 0.5～3h
-1, hydrogen to oil volume ratio is 400～5000, preferred 500～2000.The operational condition of step (2) and step (1) can be identical, also can be different.One or more mixtures in heavy hydrogenated cracking stock described in the step (2) such as vacuum distillate (VGO), atmospheric gas oil (AGO), deasphalted oil (DAO), the coker gas oil (CGO) etc.
The described reaction effluent of step (3) separates can select conventional separate mode.Can isolate gas, light naphthar, heavy naphtha, boat coal, diesel oil, hydrogenation tail oil etc. as required.The heavy naphtha arene underwater content is 50wt%～85wt%.The BMCI value of tail oil is generally below 15, is generally 5～15.
Method for hydrogen cracking of the present invention combines poor quality catalytic cracking diesel and two kinds of raw materials of VGO, is about to poor quality catalytic cracking diesel and VGO Unicracking-JHC, adopts suitable hydrogenation cracking flow process, two kinds of raw materials fully can be transformed, and effectively utilize.Particularly for poor quality catalytic cracking diesel, carrying out certain hydrotreatment earlier, again with the common hydrocracking of VGO, the effective cracking of polycyclic aromatic hydrocarbons wherein can be obtained the very high heavy naphtha of arene underwater content, is the fine reformer feed.The BMCI value of hydrogenation tail oil is low, is fine steam cracking system second raw material.
The present invention furthers investigate through the poor quality catalytic cracking diesel that the catalytic hydrogen transfer process is obtained, learn this poor quality catalytic cracking diesel density height, hydrogen richness is low, the polycyclic aromatic hydrocarbon content height is described, therefore if be processed as ordinary diesel oil or gasoline products, then need under the ten minutes exacting terms, with the polycyclic aromatic hydrocarbons hydrogenation, cracking, the a large amount of hydrogen of its process need consumption, quality product still can not meet the demands simultaneously, just can conform to quality requirements after need concocting with other high-quality volume production is brilliant, so vapour, the tooling cost of diesel product is very high, and it is unfavorable that the integral product quality is improved in processing enterprise.The inventive method is by studies show that in a large number, by with heavy hydrocarbon comprehensive processes such as VGO, can with the polycyclic aromatic hydrocarbons maximum be converted into the heavy naphtha of high arene underwater content, this heavy naphtha is the fine catalytic reforming raw material.By follow-up catforming process, the hydrogen that hydrogenation process can be mended in the raw material cements out, and loops back hydrogenation process and uses, and therefore has reasonableness economically.
Description of drawings
Fig. 1 is a hydrocracking process schematic flow sheet of the present invention.
Embodiment
Being hydrogenated to of the present invention relates to handled catalyzer and can be selected from the hydrotreating catalyst that adopts usually in the petroleum refining industry, generally is to be carrier with inorganic porous refractory oxide, is the hydrogenation activity component with group vib or VIII family metal component.Relatively Chang Yong hydrotreating catalyst generally is with γ-Al
2O
3Be carrier, the catalyst activity component is W, the Mo of group vib and VIII family metal component in the key element periodictable, among Ni, the Co one or more.With weight is benchmark, general WO
3Or MoO
3Content account for 10～30%, the content of NiO accounts for 3～12%.Simultaneously can contain auxiliary agents such as P, F, B.Specifically can select existing hydrotreating catalyst, also can prepare specific hydrotreating catalyst as required.Commercial hydrotreating catalyst as: the FRIPP of the HC-K of Uop Inc., HC-T, HC-P and Fushun Petrochemical Research Institute 3936,3996, FF-16, FF-26 etc.
Hydrocracking catalyst involved in the present invention is to comprise any suitable hydrocracking catalyst of prior art, the dual-function catalyst that it is made up of hydrogenation component and acidic components, the hydrogenation activity component is to be selected from group vib and VIII family metal component in the periodic table of elements, and acidic components are zeolite and/or amorphous silicon aluminium etc.Its carrier mainly is inorganic refractory oxides such as pure aluminium silicate, Magnesium Silicate q-agent, aluminum oxide, and the dispersion on the inorganic refractory oxide etc.Zeolite catalyst: add modification Y type, in modification β type and the modified zsm-5 zeolite one or more are as acidic components, and the hydrogenation activity component is to be selected from W, the Mo of group vib in the periodic table of elements or VIII family metal component, among Ni, the Co one or more.With weight is benchmark, and the general weight of molecular sieve component on catalyzer is 3～70%, WO
3Or MoO
3Content account for 15～30%, the content of NiO accounts for 3～10%.If use amorphous catalyst, then acid sial is as acidic components, and the hydrogenation activity component is to be selected from W, the Mo of group vib in the periodic table of elements or VIII family metal component, among Ni, the Co one or more.With weight is benchmark, and the weight of general acid sial on catalyzer is 35～75%, WO
3Or MoO
3Content account for 10～40%, the content of NiO accounts for 1～10%.Specifically can select existing hydrocracking catalyst, also can prepare specific hydrocracking catalyst as required.Commercial hydrocracking catalyst as: the HC-12 of Uop Inc., HC-14 and Fushun Petrochemical Research Institute 3905,3955,3976, FC-12, FC-24, FC-26, FC-28 etc.
The present invention recommends to adopt following hydrocracking catalyst, and this catalyzer comprises following component:
Tungsten oxide 99.999 and/or molybdenum oxide 12wt%～30wt%;
Nickel oxide and/or cobalt oxide 3wt%～6wt%;
Y zeolite 10wt%～75wt% is preferably 30wt%～60wt%;
Refractory inorganic oxides 10wt%～60wt%.
The character of described hydrocracking catalyst is as follows: specific surface is 300～500m
2/ g, pore volume are 0.20～0.45ml/g.
Wherein the character of employed Y zeolite is as follows: SiO
2/ Al
2O
3Mol ratio is 6.0～15.0, is preferably 9.0～12.0, and lattice constant is 2.436～2.444nm, and sodium oxide content is lower than 0.2wt%.Y zeolite is NH
4Further again hydrothermal treatment consists obtained after NaY type molecular sieve was handled with the hexafluorosilicic acid aqueous ammonium.The hydrothermal treatment consists process can be carried out molecular sieve separately, also can will handle jointly after molecular sieve and other material mixing.Hydrothermal treatment consists can adopt common treatment condition, also can depress at suitable ammonia branch and carry out hydrothermal treatment consists.
Described refractory inorganic oxides is one or more in aluminum oxide, silicon oxide, the amorphous aluminum silicide, preferred aluminum oxide and/or amorphous aluminum silicide, and wherein aluminum oxide comprises macroporous aluminium oxide and little porous aluminum oxide.Can also comprise conventional auxiliary agent in the catalyzer, as fluorine, titanium, phosphorus, boron etc.Weight with catalyzer is benchmark, macroporous aluminium oxide 0～35wt%, aperture aluminum oxide 10～25wt%, amorphous aluminum silicide 0～5wt%.Macroporous aluminium oxide has following character usually: pore volume is 0.8～1.1ml/g, surface-area 300～450m
2/ g.Little porous aluminum oxide has following character usually: pore volume is 0.4～0.6ml/g, surface-area 180～340m
2/ g.Amorphous aluminum silicide has following character usually: dioxide-containing silica is 10wt%～60wt%, and pore volume is 0.5～1.1ml/g, surface-area 220～560m
2/ g.
The hydrocracking catalyst that the present invention recommends can adopt two kinds of method preparations, one is as follows: the Y zeolite precursor is carried out hydrothermal treatment consists, wherein the hydrothermal treatment consists condition is as follows: temperature is 400～700 ℃, preferred 500～600 ℃, pressure is 0.05～0.2MPa, treatment time is 0.5～3 hour, obtains Y zeolite; With Y zeolite and the tackiness agent mixing, extrusion, the moulding that are made by little porous aluminum oxide, dilute nitric acid solution peptization, drying and roasting get support of the catalyst more again, and wherein selectivity adds macroporous aluminium oxide and/or amorphous aluminum silicide in the mixing process; With the solution impregnated catalyst carrier that contains reactive metal, hydrocracking catalyst of the present invention is made in drying and roasting.Described hydrothermal treatment consists can adopt water vapor or ammonia-steam-treated, and wherein during ammonia-steam-treated, the ammonia dividing potential drop is 0.005～0.05MPa.
The preparation method's of the hydrocracking catalyst that the present invention recommends is two as follows: with Y zeolite precursor and the tackiness agent mixing, extrusion, the moulding that are made by little porous aluminum oxide, dilute nitric acid solution peptization, wherein selectivity adds macroporous aluminium oxide and/or amorphous aluminum silicide in the mixing process; With water vapor or ammonia-above-mentioned forming composition of water vapor pyroprocessing, treatment condition are as follows: 400～700 ℃ of temperature, preferred 500～600 ℃, pressure is 0～0.2MPa, wherein the ammonia dividing potential drop is 0～0.05MPa, and the treatment time is 0.5～3.0 hour, makes carrier; With the solution impregnated catalyst carrier that contains reactive metal, hydrocracking catalyst of the present invention is made in drying and roasting.After wherein containing the mixture of Y zeolite precursor with water vapor or ammonia-pyroprocessing, the Y zeolite precursor changes Y zeolite into.Extrusion in above-mentioned two kinds of catalyst preparation process, drying, dipping, roasting etc. are method well-known to those skilled in the art.
Described Y zeolite precursor is to handle NH with the hexafluorosilicic acid aqueous ammonium
4NaY type molecular sieve obtains, and concrete preparation method is as follows: with raw material NH
4NaY type molecular sieve adds water and makes slurries, and wherein per 100 milliliters of slurries contain 5～30 gram raw material Y zeolites; Under the agitation condition, slurries are warming up to 50～120 ℃, in above-mentioned slurries, directly slowly add hexafluorosilicic acid aqueous ammonium or crystal then, add-on is that per 100 gram Y zeolite raw materials add 10～50 gram ammonium hexafluorosilicate, by per hour per 100 restraining the speed adding that the Y zeolite raw materials add 5～30 gram ammonium hexafluorosilicate, reaction mixture after ammonium hexafluorosilicate adds is kept 50～120 ℃ and is continued to stir 0.1～24 hour, product to gained is fluorine (silicon) ammonium aluminate sodium crystal and Y zeolite, through settlement separate fluorine (silicon) the ammonium aluminate sodium crystal of removing, obtain the Y zeolite precursor.Raw material NH wherein
4NaY type molecular sieve is the product of industrial NaY through the ammonium exchange, and requiring its sodium oxide weight content is less than 5%, SiO
2/ Al
2O
3Mol ratio is 3.5～7.0.
Above-mentioned Modified Zeolite Y is handled through ammonium hexafluorosilicate, can keep on the non-destructive basis of molecular sieve crystal phase structure, improve the silica alumina ratio of molecular sieve, increase stability, after passing through hydrothermal treatment consists adjustment sheet surface properties again, have higher activity and selectivity, can effectively improve cracking activity, because crystal phase structure is complete, more helps the middle runnings cracking and produce naphtha fraction simultaneously.Use has the hydrocracking catalyst of above-mentioned character can realize purpose of the present invention more fully.I.e. this hydrocracking catalyst virtue that can be effectively the catalytic cracking diesel oil of poor quality be converted into homogenous quantities effectively very high heavy naphtha of diving, the BMCI value of hydrogenation tail oil is very low simultaneously, is the raw material of good preparing ethylene by steam cracking.The catalyzer of the inventive method and recommendation can make the catalytic cracking diesel oil that can't produce qualified clean fuel inferior be converted into high-quality industrial chemicals, has not only made full use of raw material, has also improved value-added content of product greatly, has good economical effectiveness.Following mask body is prepared several molecular sieves and hydrocracking catalyst.
Y zeolite prepares embodiment
Take by weighing raw material NH
4(the ammonium exchange degree is 80% to NaY type molecular sieve, calcination loss of weight 27.1%, SiO
2/ Al
2O
3Mol ratio is 5.3, sodium oxide content is 4.0wt%) 2057.6 grams, add 9 liters of distilled water and make slurries, and the heating slurries are warming up to 95 ℃ under agitation condition; In above-mentioned slurries, drip solution by 495.0 gram ammonium hexafluorosilicate and the preparation of 3500 ml distilled waters, dripped off with 2 hours, continue to stir 2 hours at 95 ℃ then, stop to stir leave standstill about 10 minutes after, isolate settled fluorine (silicon) ammonium aluminate sodium crystal with decantation, and after washing, drying, obtain Y zeolite precursor A1.
Take by weighing raw material NH
4(the ammonium exchange degree is 75% to NaY type molecular sieve, calcination loss of weight 26%, SiO
2/ Al
2O
3Mol ratio is 4.5, sodium oxide content is 4.0wt%) 270 grams, add 1.2 liters of distilled water and make slurries, and the heating slurries are warming up to 95 ℃ under the backflow agitation condition, then under 95 ℃ of constant temperature reflux conditionss, added 1 time with per 5 minutes, the speed that at every turn adds 2.5g is added to 90 gram ammonium hexafluorosilicate crystal in the above-mentioned slurries, and rear slurry continues to stir 2 hours under 95 ℃ of constant temperature reflux conditionss, stop to stir leave standstill about 10 minutes after, isolate settled fluorine (silicon) ammonium aluminate sodium crystal with decantation, and after washing, drying, obtain Y zeolite precursor A2.
Hydrocracking catalyst prepares embodiment 1
Present embodiment prepares hydrocracking catalyst I, and concrete steps are as follows:
(1) with Y zeolite precursor A1 through hydrothermal treatment consists, wherein the hydrothermal treatment consists condition is as follows: temperature is 600 ℃, water partial pressure is 0.1MPa, the treatment time is 1 hour, obtains Y zeolite I;
(2) get 153.5 gram step (1) gained Y zeolite I, (pore volume 0.47ml/g, specific surface area is 280m by the little porous aluminum oxide of 120 grams
2/ g), the tackiness agent that makes of 0.2N dilute nitric acid solution 440ml peptization mixes, after extrusion, moulding, again through 110 ℃ of dryings 5 hours, 600 ℃ of roastings 6 hours support of the catalyst;
(3) support of the catalyst that obtains with the aqueous solution impregnation steps (2) that contains molybdenum and nickel, through 110 ℃ of dryings 5 hours, hydrocracking catalyst I of the present invention was made in 500 ℃ of roastings 5 hours.
Hydrocracking catalyst prepares embodiment 2
Present embodiment prepares hydrocracking catalyst II, and concrete steps are as follows:
(1) with 170gY type molecular sieve precursor A1 and the tackiness agent that makes by the little porous aluminum oxide of 80g, dilute nitric acid solution peptization (with implementing 2) mixing, extrusion, moulding;
(2) with the forming composition of ammonia-water vapor high temperature processing step (1) gained, treatment condition are as follows: 550 ℃ of temperature, pressure are 0.1MPa, and wherein the ammonia dividing potential drop is 0.01MPa, and the treatment time is 1 hour, makes carrier, wherein contains Y zeolite II;
(3) support of the catalyst that obtains with the aqueous solution impregnation steps (2) of tungstenic and nickel, through 110 ℃ of dryings 5 hours, hydrocracking catalyst II of the present invention was made in 500 ℃ of roastings 5 hours.
Hydrocracking catalyst prepares embodiment 3
Present embodiment prepares hydrocracking catalyst III, and concrete steps are as follows:
(1) with Y zeolite precursor A2 through water vapor thermal treatment, wherein treatment condition are as follows: temperature is 550 ℃, water partial pressure is 0.2MPa, the treatment time is 1 hour, obtains Y zeolite II;
(2) get 228 gram step (1) gained Y zeolite III, (silica content is 40wt%, pore volume 0.64ml/g, surface-area 310m by tackiness agent (with embodiment 2), the 46g amorphous aluminum silicide of 100g aperture aluminum oxide preparation
2/ g) mix, after extrusion, moulding, again through 100 ℃ of dryings 6 hours, 600 ℃ of roastings 5 hours support of the catalyst;
(3) support of the catalyst that obtains with the aqueous solution impregnation steps (2) that contains molybdenum and nickel, through 110 ℃ of dryings 5 hours, hydrocracking catalyst III of the present invention was made in 500 ℃ of roastings 5 hours.
Hydrocracking catalyst prepares embodiment 4
Present embodiment prepares hydrocracking catalyst IV, and concrete steps are as follows:
(1) with 274gY type molecular sieve precursor A2 and the tackiness agent that makes by the little porous aluminum oxide of 80g, dilute nitric acid solution peptization (with implementing 2) mixing, extrusion, moulding;
(2) with the forming composition of ammonia-water vapor high temperature processing step (1) gained, treatment condition are as follows: 550 ℃ of temperature, pressure are 0.1MPa, and wherein the ammonia dividing potential drop is 0.01MPa, and the treatment time is 1 hour, makes carrier, wherein contains Y zeolite IV;
(3) support of the catalyst that obtains with the aqueous solution impregnation steps (2) of tungstenic and nickel, through 110 ℃ of dryings 5 hours, hydrocracking catalyst IV of the present invention was made in 500 ℃ of roastings 5 hours.
The character of Y zeolite in each hydrocracking catalyst of table 1
| The Y zeolite numbering | I | II | III | IV |
| SiO 2/Al 2O 3Mol ratio | 11.85 | 11.74 | 10.75 | 10.68 |
| Lattice constant, nm | 2.438 | 2.437 | 2.440 | 2.439 |
| Sodium oxide, wt% | 0.06 | 0.05 | 0.16 | 0.16 |
| Relative crystallinity, % | 99 | 72 | 103 | 78 |
The composition and the character of each embodiment gained hydrocracking catalyst of table 2
| The catalyzer numbering | I | II | III | IV |
| Form wt% | ||||
| Nickel oxide | 5.1 | 5.7 | 4.6 | 4.0 |
| Tungsten oxide 99.999 | - | 21.5 | - | 23.5 |
| Molybdenum oxide | 16.8 | - | 14.8 | - |
| Y zeolite | 44.0 | 50.2 | 48.6 | 56.2 |
| Amorphous aluminum silicide | - | - | 10.2 | - |
| Aluminum oxide | Surplus | Surplus | Surplus | Surplus |
| Character | ||||
| Specific surface, m 2/g | 395 | 397 | 400 | 410 |
| Pore volume, ml/g | 0.29 | 0.31 | 0.28 | 0.30 |
Further specify the present invention program and effect below in conjunction with Application Example.The catalyzer FF-26 that wherein relates to is a hydrotreating catalyst, Fushun Petrochemical Research Institute's development, and Gong Quan chemical company in Shandong produces, and main character sees Table 3.Stock oil character sees Table 4, concrete operations condition and the results are shown in Table 5.Wherein the boiling range of heavy naphtha is 65～177 ℃, and the cut point of kerosene and diesel oil is 282 ℃, and the cut point of tail oil is 370 ℃.Product yield is benchmark (raw material is all liquid phase feed sums) with stock oil.
The main character of table 3 hydrotreating catalyst FF-26
| Catalyzer | FF-26 |
| Carrier | γ-Al 2O 3 |
| Reactive metal is formed, wt% | |
| MoO 3+NiO | 29 |
| Auxiliary agent P 2O 5，wt％ | 4 |
| Pore volume/mlg -1 | 0.34 |
| Specific surface area/m 2·g -1 | 175 |
| Tap density/gcm -3 | 0.97 |
Table 4 stock oil character
| Stock oil | Iran VGO | Catalytic cracking diesel oil 1 | Catalytic cracking diesel oil 2 |
| Density (20 ℃)/gcm -3 | 0.9135 | 0.9458 | 0.9694 |
| Boiling range/℃ | 350～545 | 168～369 | 202～361 |
| Sulphur content, m% | 1.74 | 1.12 | 1.18 |
| Nitrogen content/μ gg -1 | 1535 | 915 | 1620 |
| Aromatic hydrocarbons, m% | 43.8 | 82.0 | 93.1 |
| Cetane value | - | 16.6 | 13.5 |
Enter hydrocracking behind table 5 diesel oil hydrofining with after VGO mixes, once pass through flow process
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The diesel oil hydrofining processing condition | ||||
| Stock oil | Catalytic cracking diesel oil 2 | Catalytic cracking diesel oil 1 | Catalytic cracking diesel oil 1 | Catalytic cracking diesel oil 2 |
| Catalyzer | FF-26 | FF-26 | FF-26 | FF-26 |
| Pressure/MPa | 15.0 | 15.0 | 12.0 | 8.0 |
| Temperature/℃ | 360 | 375 | 360 | 370 |
| Air speed/h -1 | 2.0 | 2.5 | 1.8 | 2.0 |
| Hydrogen to oil volume ratio | 500∶1 | 500∶1 | 700∶1 | 400∶1 |
| Treated oil nitrogen content/μ gg -1 | 110.5 | 30.5 | 90.2 | 158.7 |
| The treated oil aromaticity content, m% | 58.7 | 58.7 | 55.2 | 65.3 |
| The hydrocracking process condition | ||||
| Catalytic cracking diesel oil weight ratio behind Iran VGO and the hydrogenation | 80∶20 | 70∶30 | 65∶35 | 80∶20 |
| Catalyzer | FF-26/ hydrocracking catalyst I | FF-26/ hydrocracking catalyst II | FF-26/ hydrocracking catalyst III | FF-26/ hydrocracking catalyst IV |
| The catalyst loading volume ratio | 69∶31 | 69∶31 | 60∶40 | 60∶40 |
| Pressure/MPa | 15.0 | 15.0 | 12.0 | 8.0 |
| Temperature/℃ | 375/383 | 372/385 | 370/375 | 373/378 |
| Air speed/h -1 | 1.1/2.4 | 1.1/2.4 | 1.4/2.1 | 1.0/1.5 |
| Hydrogen to oil volume ratio | 900∶1 | 900∶1 | 900∶1 | 900∶1 |
| Per pass conversion, m% | 80.0 | 85.0 | 70.0 | 80.0 |
| Product | ||||
| The heavy naphtha yield, m% | 38.6 | 37.7 | 24.2 | 41.6 |
| The heavy naphtha virtue is dived | 71.3 | 71.0 | 73.6 | 75.4 |
| The boat yield of coal, m% | 19.4 | 22.4 | 22.0 | 17.9 |
| Boat coal smoke point/mm | 26 | 25 | 24 | 23 |
| Diesel yield, m% | 9.7 | 17.7 | 16.5 | 10.2 |
| Diesel cetane-number | 55.8 | 53.9 | 51.6 | 51.1 |
| The tail oil yield, m% | 20.2 | 14.8 | 30.2 | 19.9 |
| Tail oil BMCI value | 8.9 | 11.2 | 13.5 | 14.6 |
Claims (17)
1, a kind of combined hydrocracking method is produced the heavy naphtha of high arene underwater content, comprises following process:
(1) under hydroprocessing condition, with poor quality catalytic cracking diesel by containing the bed of hydrotreating catalyst;
(2) reaction effluent that obtains of step (1) and the mixture of heavy hydrogenated cracking stock, under hydrocracking condition by containing the bed of hydrotreating catalyst and hydrocracking catalyst;
(3) reaction product that obtains of step (2) is separated, and obtains various product light-end productss and hydrogenation tail oil.
2, in accordance with the method for claim 1, it is characterized in that the described poor quality catalytic cracking diesel of step (1) is a catalytic cracking diesel oil heavy, that residual oil catalytic cracking obtains.
3, in accordance with the method for claim 1, it is characterized in that the described poor quality catalytic cracking diesel of step (1) is the catalytic cracking diesel oil that adopts the catalytic cracking of hydrogen transference technology to obtain.
4, in accordance with the method for claim 1, it is characterized in that more than 20 ℃ of density 0.90g/ml of the described poor quality catalytic cracking diesel of step (1), more than the aromaticity content 60wt%, cetane value about 20.
5, in accordance with the method for claim 1, it is characterized in that 20 ℃ of density of the described poor quality catalytic cracking diesel of step (1) are 0.90～0.99g/ml, aromaticity content is 60wt%～97wt%, and cetane value is 12～30.
6, in accordance with the method for claim 1, it is characterized in that 20 ℃ of density of the described poor quality catalytic cracking diesel of step (1) are 0.92～0.96g/ml, aromaticity content is 70wt%～90wt%, and cetane value is 15～25.
7, in accordance with the method for claim 1, it is characterized in that the described hydroprocessing condition of step (1) is: reaction pressure is 3～20MPa, and temperature of reaction is 300～480 ℃, and volume space velocity is 0.1～8h during liquid
-1Hydrogen to oil volume ratio is 200～5000.
8, in accordance with the method for claim 1, it is characterized in that the described hydroprocessing condition of step (1) is: reaction pressure is 5～16MPa, and temperature of reaction is 330～440 ℃, and volume space velocity is 0.5～3h during liquid
-1, hydrogen to oil volume ratio is 500～2000.
9, in accordance with the method for claim 1, it is characterized in that the described hydrocracking condition of step (2) is: reaction pressure is 3～20MPa, and temperature of reaction is 300～480 ℃, and volume space velocity is 0.2～8h during total liquid
-1, hydrogen to oil volume ratio is 400～5000.
10, in accordance with the method for claim 1, it is characterized in that the described hydrocracking condition of step (2) is: reaction pressure is 5～17MPa, and temperature of reaction is 330～440 ℃, and volume space velocity is 0.5～3h during total liquid
-1, hydrogen to oil volume ratio is 500～2000.
11, in accordance with the method for claim 1, it is characterized in that the described heavy hydrogenated cracking stock of step (2) is one or more the mixture in vacuum distillate, atmospheric gas oil, deasphalted oil and the coker gas oil etc.
12, in accordance with the method for claim 1, it is characterized in that the described reaction effluent of step (3) is separated into gas, light naphthar, heavy naphtha, boat coal, diesel oil and hydrogenation tail oil.
13, in accordance with the method for claim 1, it is characterized in that described hydrocracking catalyst comprises following component:
Tungsten oxide 99.999 and/or molybdenum oxide 12wt%～30wt%;
Nickel oxide and/or cobalt oxide 3wt%～6wt%;
Y zeolite 10wt%～75wt%;
Refractory inorganic oxides 10wt%～60wt%.
14, in accordance with the method for claim 13, it is characterized in that described Y zeolite content is 30wt%～60wt%.
15, in accordance with the method for claim 13, it is characterized in that described hydrocracking catalyst specific surface is 300～500m
2/ g, pore volume are 0.20～0.45ml/g.
16, in accordance with the method for claim 13, it is characterized in that the character of described Y zeolite is as follows: SiO
2/ Al
2O
3Mol ratio is 6.0～15.0, is preferably 9.0～12.0, and lattice constant is 2.436～2.444nm, and sodium oxide content is lower than 0.2wt%.
17, in accordance with the method for claim 13, it is characterized in that described Y zeolite is NH
4Further again hydrothermal treatment consists obtained after NaY type molecular sieve was handled with the hexafluorosilicic acid aqueous ammonium.
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| CN102688770A (en) * | 2012-04-28 | 2012-09-26 | 中国科学院青岛生物能源与过程研究所 | Aromatics hydrogenation catalyst and preparation method and application of aromatics hydrogenation catalyst |
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| CN102688770A (en) * | 2012-04-28 | 2012-09-26 | 中国科学院青岛生物能源与过程研究所 | Aromatics hydrogenation catalyst and preparation method and application of aromatics hydrogenation catalyst |
| CN103805247A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Combination method used for processing inferior diesel oil |
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| CN104258870A (en) * | 2014-10-16 | 2015-01-07 | 中国科学院山西煤炭化学研究所 | Catalyst for hydrocracking polycyclic aromatic hydrocarbon compound as well as preparation method and application of catalyst |
| CN109777500A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of two-segment hydrocracking method of gas-liquid counter current |
| CN109777500B (en) * | 2017-11-14 | 2021-01-05 | 中国石油化工股份有限公司 | Gas-liquid countercurrent two-stage hydrocracking method |
| CN109988635A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of hydrotreating and hydrocracking combined process |
| CN109988635B (en) * | 2017-12-29 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrotreatment and hydrocracking combined process |
| CN110628462A (en) * | 2019-10-14 | 2019-12-31 | 中国石油化工股份有限公司 | Hydrocracking and catalytic cracking combined process and device |
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| CN113244947A (en) * | 2021-05-21 | 2021-08-13 | 晋中学院 | High-cetane-number diesel catalyst and preparation method and application thereof |
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