CN104073293B - A kind of method that heavy hydrocarbon oil is hydrocracked - Google Patents
A kind of method that heavy hydrocarbon oil is hydrocracked Download PDFInfo
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Abstract
The present invention relates to a kind of method that heavy hydrocarbon oil is hydrocracked, the hydrocracking catalyst that the method uses is made up of β zeolite 2%～20%, refractory inorganic oxides 20%～70%, VI B family metal oxide 10%～25%, VIII family metal oxide 3%～10%；Master module agent tetraethyl ammonium halide, aluminum source, silicon source is added in sodium hydroxide solution, by gained mixture low temperature maturation 2h～16h at 40 DEG C～100 DEG C, reactant mixture is placed on the multiple sieve plate in reactor, water and the mixture of low carbon number organic amine auxiliary template agent is added bottom reactor, crystallization 24h～60h at 130 DEG C～160 DEG C, through filtering, washing and be dried, obtain β zeolite；This method effectively reduces the preparation cost of catalyst, improves the low temperature flow of intermediate oil, improves the yield of intermediate oil.
Description
Technical field
The present invention relates to a kind of method that heavy hydrocarbon oil is hydrocracked, use the hydrogenation containing β zeolite to split
Change catalyst, be light ends oil particularly high-grade low-freezing by heavy hydrocarbon oil cracking under hydrogen effect
Diesel oil.
Background technology
Hydrocracking technology is one of important means of heavy oil deep processing, have adaptability to raw material strong,
The plurality of advantages such as processing scheme is flexible, liquid product yield is high, good product quality, the most progressively develop
Become modern oil refining enterprise and be directly produced clear gusoline and high-quality industrial chemicals by inferior, heavy charge
Unique clearer production technology, it has also become the oil refining core apparatus run neck and neck with catalytic cracking.UOP、
The company both at home and abroad such as CLG, Shell, Akzo Nobel, IFP, Sinopec has been developed that maximum
The series that production intermediate oil, flexibly fecund Petroleum/jet fuel/diesel oil etc. differ from one another is urged
Agent and technique, greatly accelerate the development process of hydrocracking technology.
The core of hydrocracking technology is hydrocracking catalyst, develops the hydrogenation that specific aim is higher
Cracking catalyst is one of key of meeting the market requirement, promotion hydrocracking technology development.In early days
Hydrocracking catalyst be to use for reference the alumina silicate catalyst of catalytic cracking and coal and coal tar gas phase
The metal sulfide catalyst of hydrogenation, cracking activity and the hydrogenation of metal sulfide of aluminium silicate
Activity combines composition hydrocracking catalyst, later Union company carried out with molecular sieve be
The R&D work of the hydrocracking catalyst of carrier, and it was first utilized in Unicracking in 1964
Produce Petroleum on hydrocracking unit, establish hydrocracking catalyst development foundation.But in early days
Catalyst due to acid function strong, reaction temperature is relatively low, and pore structure and peracidity cause catalyst
Activity is higher, is conducive to fecund Petroleum but is unfavorable for fecund intermediate oil.Later, by right
Molecular sieve carries out advanced treating, reduces acid site number, suppression second pyrolysis reaction；Increase by 5～20nm
The secondary pore of scope, makes pore size distribution be conducive to the diffusion of reactant and product；Strengthening hydrogenation merit simultaneously
With the mating of acid function, thus the hydrocracking catalyst of various satisfied different demands can be occurred in that.
At present, the catalyst Middle molecule sieve-type catalyst in commercial Application account for absolute advantages, wherein
Partial catalyst has reached the level of amorphous silica-alumina for the selectivity of intermediate oil, but
Activity increases substantially.
The hydrocracking catalyst used on commercial plant at present, major part employs various difference and changes
Property the degree of depth Y zeolite, this molecular sieve, by modification, has higher to kerosene and the choosing of diesel oil
Selecting property, and catalyst activity is higher, but it is disadvantageous in that alkane stereoselectivity poor,
So the kerosene produced and diesel low-temperature liquidity are poor, it is unfavorable for high-output qulified low-coagulation diesel oil, with
Cold season in winter, there was a certain distance in market to the urgent needs of high-grade low-freezing diesel oil.
β zeolite is the catalysis material the most gradually drawn attention in oil refining catalyst field, has
Special twelve-ring three-dimensional open-framework, compares other for adding to the selectivity of alkane reaction
The molecular sieve of hydrogen Cracking catalyst is higher, thus is conducive to obtaining the crackate of low condensation point.
US5447623 discloses a kind of hydrocracking catalyst using β Yu Y mixed zeolite, wherein
The SiO of β zeolite2/Al2O3Mol ratio is desirably no more than 40, in 20～30, β: Y is preferably
1:2～2:1, the content of every kind of zeolite is 2.5%～10%, this catalyst can be used for produce gasoline and in
Between distillate.It addition, the patents such as US6670295B2,7585405B2 the most all have employed SiO2/Al2O3
Mol ratio be 25～about 30 β zeolite prepare hydrocracking catalyst.Generally, above-mentioned patent
The β Zeolite related to is relatively low, and acid site number is more, is unfavorable for fecund intermediate oil.
CN1210881A discloses a kind of super-hydrophobic beta-molecular sieve modified with Low acid and amorphous silicon
Aluminum is that carrier material makes hydrocracking catalyst, and wherein beta-molecular sieve content is 10%～30%, nothing
Amorphous silicon-alumina 10%～50%.The β zeolite that this invention uses, employs the silica alumina ratio 25 of commercialization
β zeolite, as raw material, then carries out ammonium exchange, then be dried, roasting, acid dealuminzation and hydrothermal treatment consists,
Prepare the β zeolite finished product of 30～90.Because modification route is longer, so preparation time is longer, system
Standby relatively inefficient.
CN1107710 refer to a kind of with 5%～30% β zeolite and 5%～30%Y zeolite for acid group
The medium oil hydrocracking catalyst divided, this catalyst effectively reduces the condensation point of diesel oil, with list
The catalyst of pure use Y molecular sieve is compared, condensation point of diesel oil 3～8 DEG C.But the β boiling that this invention uses
Stone first has to the synthesizing Si-Al zeolite materials than 25～30, is then separated by mother solution and merges with ammonium exchange
One step is carried out, then be dried, roasting, carry out acid dealuminzation and hydrothermal treatment consists as required, prepare 30～
The β zeolite finished product of 90.When the feature of this invention is β zeolite synthesis, mother solution separates and merges with ammonium exchange
One step is carried out, thus decreases the time that mother solution separates, but identical with CN1210881A, is directed to
To the post-modification of β zeolite, so preparation efficiency is the most relatively low.
Summary of the invention
It is an object of the invention to provide a kind of method that heavy hydrocarbon oil is hydrocracked, by using one
The β zeolite type hydrocracking catalyst plant low cost, efficiently synthesizing, splits heavy hydrocarbon oil at hydrogenation
Changing cracking under the effect of catalyst and hydrogen is light ends oil particularly high-grade low-freezing diesel oil.First
By heavy hydrocarbon oil and hydrogen Hybrid Heating or individually hydrogen is heated, heavy hydrocarbon oil and other material
Mix with hydrogen again after heat exchange, use suitable technological process and operating condition, sequentially pass through pre-place
Reason catalyst, Cracking catalyst and rear catalyst for refining, by heavy hydrocarbon oil under the effect of catalyst
It is converted into light, heavy naphtha, kerosene, diesel oil and tail oil.
Heretofore described heavy hydrocarbon oil includes coker gas oil, vacuum gas oil (VGO), normal pressure gas
The charging of the various heavy hydrocarbons such as oil, dewaxed oil and compound thereof, boiling range scope at 200 DEG C～580 DEG C,
Nitrogen content ≯ 2000 μ g/g, sulfur content 0.05%～3%, carbon residue ≯ 0.7%, asphalitine ＜ 0.02%,
Tenor ≯ 3 μ g/g.
Heretofore described technological process is preferably with single hop serial hydrocracking technological process.Described
Pretreatment catalyst, Cracking catalyst and rear catalyst for refining pre-sulfur in the device generally used
After change process, in reaction temperature 300 DEG C～500 DEG C, hydrogen dividing potential drop 8MPa～20MPa, hydrogen oil volume
Than volume space velocity 0.5hr when 500:1～2000:1, liquid-1～3.0hr-1Under process conditions, carry out weight
Matter hydrocarbon oil hydrogenation cracking.
In the present invention, pretreatment catalyst and rear catalyst for refining are this area conventional catalyst, best
Essence after the PHT-01 pretreatment catalyst researched and developed for Petroleum Chemical Engineering Institute of CNPC and PHT-01
Catalyst processed, it is desirable at reaction temperature 300 DEG C～500 DEG C, hydrogen dividing potential drop 8MPa～20MPa, hydrogen oil
Volume space velocity 0.5hr when volume ratio 500:1～2000:1, liquid-1～3.0hr-1Under process conditions, essence
System generates the nitrogen content ≯ 50 μ g/g of oil.
In the present invention, hydrocracking catalyst is a kind of hydrocracking catalyst containing β zeolite, catalyst
Count by weight percentage: β zeolite 0%～35%, preferably 2%～20%, preferably 5%～15%；
Refractory inorganic oxides 20%～70%, preferably 40%～70%, preferably 55%～68%；VI B race
Metal-oxide 10%～25%, preferably 15%～25%, preferably 18%～25%；VIII race's metal oxygen
Compound 3%～10%, preferably 4%～8%, preferably 5%～8%.
The inorganic refractory inorganic oxide that in the present invention, hydrocracking catalyst is used, can include
One or more in macropore amorphous silicon aluminium, macroporous aluminium oxide, little porous aluminum oxide, the most greatly
Hole amorphous silicon aluminium and the mixture of little porous aluminum oxide, preferably macropore amorphous silicon aluminium, macropore oxygen
Change aluminum, three kinds of hopcalites of little porous aluminum oxide.Wherein, macropore amorphous silicon aluminium is as urging
The acid helper component (β zeolite is main acidic components) of agent and main carriers component, dispersion
Hydrogenation metal component and β zeolite acidity component, SiO in this material2Weight content be generally 25%～
60%, preferably 30%～60wt%, preferably 40%～55wt%；Specific surface area is generally 250m2/ g～
550m2/ g, preferably 280m2/ g～500m2/ g, preferably 300m2/ g～450m2/g；Pore volume is
0.5ml/g～1.2ml/g, preferably 0.6ml/g～1.1ml/g are preferably 0.8ml/g～1.0ml/g.
Macroporous aluminium oxide as assistant carrier component, can improve further catalyst hydrogenation metal component and
The dispersibility of β zeolite acidity component, its pore volume is 0.7ml/g～1.2ml/g, is preferably
0.75ml/g～1.2ml/g, preferably 0.85ml/g～1.0ml/g；Specific surface area is 150m2/ g～
450m2/ g, preferably 250m2/ g～450m2/ g, preferably 260m2/ g～350m2/g.Aperture aoxidizes
Aluminum uses generally as binding agent but it also may adds directly as powder material, improves catalyst
Intensity, its pore volume is 0.2ml/g～0.7ml/g, preferably 0.3ml/g～0.7ml/g, best
For 0.4ml/g～0.7ml/g；Specific surface area is 150m2/ g～350m2/ g, preferably 150m2/ g～
280m2/ g, preferably 200m2/ g～250m2/g。
The β zeolite that in the present invention, hydrocracking catalyst is used is to use the solid double-template method of vapour to prepare
, SiO2/Al2O3Mol ratio is 30～200, preferably 30～120, preferably 40～80；Oxygen
Changing sodium content is ＜ 0.5%, preferably ＜ 0.2%, preferably ＜ 0.05%；Specific surface area is 300m2/ g～
800m2/ g, preferably 350m2/ g～700m2/ g, preferably ＜ 500m2/ g～700m2/g；Pore volume is
0.20ml/g～0.45ml/g, preferably 0.25ml/g～0.45ml/g, preferably 0.28ml/g～
0.40ml/g。
Preparation method is as follows:
Hydrocracking catalyst is count by weight percentage: β zeolite is 2%～20%；The inorganic oxygen of refractory
Compound 20%～70%；VI B family metal oxide 10%～25%；VIII family metal oxide 3%～10%；
β zeolite preparation method is as follows:
Adding master module agent tetraethyl ammonium halide in sodium hydroxide solution, molecular formula is TEA+X-, its
One or both mixture in middle X=Cl, Br, are stirring evenly and then adding into aluminum source, and stirring and dissolving is to thoroughly
Bright addition silicon source, continues stirring 1h～4h, by old for gained mixture low temperature at 40 DEG C～100 DEG C
Change 2h～16h, gained initial reaction mixture is placed on the multiple sieve plate in reactor, instead
Answer bottom portion to add water and the mixture of low carbon number organic amine auxiliary template agent, heat up, 130 DEG C～
Crystallization 24h～60h at 160 DEG C, products therefrom, through filtering, washing and be dried, obtains β zeolite；
The mol ratio of synthetic system material is: SiO2/Al2O3=30～300, TEA+/SiO2=
0.05～0.30, Na2O/SiO2=0.15～0.80, H2O/SiO2=7～15；
The mol ratio of reactor bottoms material is H2O/SiO2=0.5～2.0, R/SiO2=0.08～
0.18, R is low carbon number organic amine auxiliary template agent.
The silicon source that in the present invention, β zeolite synthesis is used can be tetraethyl orthosilicate, Ludox, consolidate
The mixture of the suitable proportion of one or more in body silicic acid, solid silicone or white carbon, aluminum source
Can be the one in aluminum sulfate, sodium aluminate, aluminum isopropylate., boehmite or aluminium hydroxide or
The mixture of several suitable proportions, master module agent be tetraethyl ammonium halide such as tetraethylammonium bromide,
The mixture of a kind of or its suitable proportion in tetraethylammonium chloride, auxiliary template agent be triethylamine,
Diethylamine or the mixture of its suitable proportion, what ammonium salt exchange used can be ammonium chloride, ammonium nitrate
Or the aqueous solution of ammonium sulfate.
The β zeolite that in the present invention, hydrocracking catalyst is used is high silica alumina ratio zeolite, the most
Through the β zeolite of silica alumina ratio industrialized, identical, typically to use with organic amine as template, water
The skeleton SiO of thermal crystallisation method synthesis2/Al2O3Mol ratio is the low silica-alumina ratio beta zeolite conduct of 25～30
Raw material, prepared by the mode using hydro-thermal and/or acid treatment to combine, owing to preparation technology route is longer,
Zeolite yield reduces, so preparation cost is higher.The present invention proposes the solid double-template method of a kind of vapour and closes
The method becoming β zeolite, uses tetraethyl ammonium halide as master module agent, uses low carbon number organic amine
As auxiliary template agent, make aged to silicon source, aluminum source and template etc. in building-up process
Initial reaction mixture is placed on the sieve plate in reactor, puts into appropriate water and auxiliary in Polycondensation Reactor and Esterification Reactor
The mixed liquor of co-template, initial reaction mixture does not contact with the continuous phase of Polycondensation Reactor and Esterification Reactor, auxiliary
Co-template jointly acts on master module by water vapour under crystallization condition and making with through low temperature maturation
Initial reaction mixture, promote master module agent play guide β zeolite topological formed effect,
Auxiliary template agent also interacts with master module so that under crystallization temperature, the structure of master module agent obtains
With stable, the synthesis of beneficially β zeolite, in combination with the modulation to synthetic method, by crystalline substance
Low temperature maturation section is increased before change, this through polycondensation, the initial reaction mixture of rearrangement reaction formation,
There is higher reactivity, thus reach in cheap template system, form β boiling
The purpose of stone crystalline phase.This synthetic method is used to break away from the synthesis of β zeolite to expensive template
The dependence of agent tetraethyl ammonium hydroxide, gained β zeolite crystallinity is high, due to template used dose of price
Cheap, the most fundamentally reduce the synthesis cost of β zeolite, thus reduce the system of catalyst
Standby cost.
The molding mode of the carrier of hydrocracking catalyst that the present invention relates to is extruded moulding, and metal is born
Load mode is infusion process, and dipping method can be incipient impregnation, it is also possible to be supersaturation dipping,
Can carry out as follows:
(1) by macropore amorphous silica-alumina involved in the present invention, macroporous aluminium oxide, β zeolite by institute
Ratio is needed to add and mix homogeneously；
(2) by the binding agent prepared by little porous aluminum oxide, dilute acid soln or directly to the powder body of (1)
Middle addition dilute acid soln, kneading becomes paste；
(3) the paste extrusion described in (2) is made cylindrical carrier, it is possible to make irregular bar such as
Herba Trifolii Pratentis or Herba Galii Bungei shape；
(4) molding carrier is dried at 90 DEG C～150 DEG C 2hr～6hr, then at 400 DEG C～
Calcination activation 3hr～8hr in 700 DEG C of air atmospheres, makes carrier；
(5) preparation is containing group VIB, the impregnation liquid of group VIII metal；
(6) use incipient impregnation or supersaturation infusion process by above-mentioned impregnation liquid once or batch uploading
In catalyst carrier；
(7) carrier impregnated is dried 1hr～5hr at 80 DEG C～150 DEG C, then exists
Roasting 3hr～8hr at 400 DEG C～700 DEG C, the finished catalyst after being activated.
During molding prepared by above-mentioned catalyst, can add according to the mode known to insider
A certain proportion of extrusion aid, such as sesbania powder and polynary hydroxy acid (such as citric acid) etc..Dilute acid soln
For one or more in mineral acid and/or organic acid, preferably hydrochloric acid, nitric acid, phosphoric acid, sulphuric acid.
In the present invention, the metal used by hydrocracking catalyst is the W of group VIB, the Ni of the VIIIth race.
The method have the characteristics that used hydrocracking catalyst have employed the solid double-template legal system of vapour
Standby β zeolite is as the main acidic components of catalyst, owing to the synthesis of β zeolite has been broken away from valency
The dependence of the template tetraethyl ammonium hydroxide that lattice are expensive, template used dose cheap, so from
Fundamentally reduce the synthesis cost of β zeolite, thus reduce the preparation cost of catalyst.It addition,
Owing to β zeolite 12 ring macropore straight channel is good, so leading for alkane cracking and stereoselectivity
Cause the production of this heavy hydrocarbon oil method for hydrogen cracking and there is the features such as intermediate oil yield is high, condensation point is low,
Can apply to fecund intermediate oil Petrochemical Enterprises, particularly Northern Enterprises, high-output qulified low
Coagulation diesel oil, has broad application prospects.
Detailed description of the invention
Embodiment 1:
Take 6.75g deionized water, be added thereto to 1.50g tetraethylammonium bromide (effective content 95%),
0.48g sodium hydroxide (effective content 96%), 0.18g sodium aluminate (Al2O3Content 45%), stirring
Clarify to mixed solution, be added thereto to 3.00g silochrom (SiO2Content 96%), stir 2h,
At 80 DEG C, it is aged 12h, gained initial reaction mixture is placed in the sieve plate on reactor top,
0.85g deionized water and 0.55g triethylamine is added, at 140 DEG C on multiple sieve plate in reactor
Crystallization 24h, is drying to obtain β zeolite sample by the washing of gained sample filtering, is designated as β 1, and character is shown in
Table 1.
Embodiment 2:
Take 9.25g deionized water, be added thereto to 1.60g tetraethylammonium bromide (effective content 95%),
0.45g sodium hydroxide (effective content 96%), 0.16g sodium aluminate (Al2O3Content 45%), stirring
Clarify to mixed solution, be added thereto to 3.00g white carbon (SiO2Content 98%), stir 2h,
At 80 DEG C, it is aged 12h, gained initial reaction mixture is placed in the sieve plate on reactor top,
0.80g deionized water and 0.50g triethylamine is added, at 140 DEG C on multiple sieve plate in reactor
Crystallization 24h, is drying to obtain β zeolite sample by the washing of gained sample filtering, is designated as β 2, and character is shown in
Table 1.
Embodiment 3:
Take 6.75g deionized water, be added thereto to 2.30g tetraethylammonium bromide (effective content 95%),
0.52g sodium hydroxide (effective content 96%), 0.20g aluminum sulfate (Al2(SO4)3·18H2O, Al2O3
Content 49%), stir and clarify to mixed solution, be added thereto to 3.00g silochrom (SiO2Contain
Amount 96%), stir 2h, at 80 DEG C, be aged 12h, gained initial reaction mixture is placed in reaction
The sieve plate on still top, multiple sieve plate in a kettle. adds 0.75g deionized water and 0.65g
Triethylamine, crystallization 32h at 140 DEG C, the washing of gained sample filtering is drying to obtain β zeolite sample,
Being designated as β 3, physico-chemical property is shown in Table 1.
Table 1 beta-molecular sieve physico-chemical property
| Sample number into spectrum | β1 | β2 | β3 |
| SiO2/Al2O3Mol ratio | 60 | 70 | 50 |
| Specific surface area, m2/g | 552 | 524 | 526 |
| Total hole volume, ml/g | 0.31 | 0.30 | 0.32 |
| Average pore size, nm | 2.2 | 2.1 | 2.3 |
Embodiment 4:
By 10.0g β 1 molecular sieve, 60.0g amorphous silica-alumina (SiO2Content 34%, pore volume 0.95ml/g,
BET specific surface 380m2/ g), 10.0g macroporous aluminium oxide (pore volume 0.94ml/g, specific surface 358m2/ g)
With 5.3g sesbania powder mixed grind 30min, it is subsequently adding mix homogeneously and deposits the binding agent of 24 hours
[the little porous aluminum oxide of 20.0g (pore volume 0.36ml/g, specific surface 232m2/ g), 70.0g deionized water,
34% dust technology 8g, citric acid 3g], mix homogeneously also rolls to toothpaste-squeezable paste on small-sized banded extruder,
Be extruded into cylinder stripe shape, extrusion bar at 120 DEG C of dry 2hr, 550 DEG C of roasting 4hr of dried strip temperature programming,
Obtain carrier.(ammonium metatungstate concentration 49.97g/100ml, nickel nitrate is dense for carrier tungstenic-nickel impregnation liquid
Degree 53.88g/100ml) room temperature immersion, health preserving 2hr, 120 DEG C of dry 2hr, temperature programming 550 DEG C
Roasting 4hr, prepares catalyst I, and physico-chemical property is shown in Table 2.
Embodiment 5:
By 15.0g β 2 molecular sieve, 55.0g amorphous silica-alumina (SiO2Content 50%, pore volume 0.75ml/g,
BET specific surface 300m2/ g), 5.0g macroporous aluminium oxide (pore volume 0.94ml/g, specific surface 358m2/ g)
With 5.3g sesbania powder mixed grind 30min, it is subsequently adding mix homogeneously and deposits the binding agent of 12 hours
[the little porous aluminum oxide of 25.0g (pore volume 0.36ml/g, specific surface 232m2/ g), 70.0g deionized water,
34% dust technology 8g, citric acid 3g], mix homogeneously also rolls to toothpaste-squeezable paste on small-sized banded extruder,
Be extruded into cylinder stripe shape, extrusion bar at 120 DEG C of dry 2hr, 550 DEG C of roasting 5hr of dried strip temperature programming,
Obtain carrier.(ammonium metatungstate concentration 49.97g/100ml, nickel nitrate is dense for carrier tungstenic-nickel impregnation liquid
Degree 53.88g/100ml) room temperature immersion, health preserving 1hr, 120 DEG C of dry 2hr, temperature programming 550 DEG C
Roasting 5hr, prepares catalyst II, and physico-chemical property is shown in Table 2.
Embodiment 6:
By 8.0g β 3 molecular sieve, 57.0g amorphous silica-alumina (SiO2Content 50%, pore volume 0.75ml/g,
BET specific surface 300m2/ g), 15.0g macroporous aluminium oxide (pore volume 0.94ml/g, specific surface 358m2/ g),
The little porous aluminum oxide of 20.0g (pore volume 0.36ml/g, specific surface 232m2/ g), 5.3g sesbania powder mixed grind
30min, be subsequently adding mix homogeneously dilute acid soln (70.0g deionized water, 34% dust technology 8g,
Citric acid 3g), mix homogeneously also rolls to toothpaste-squeezable paste on small-sized banded extruder, is extruded into cylinder stripe shape,
Extrusion bar, at 120 DEG C of dry 2hr, 550 DEG C of roasting 5hr of dried strip temperature programming, obtains carrier.Carry
Body tungstenic-nickel impregnation liquid (ammonium metatungstate concentration 49.97g/100ml, nickel nitrate concentration
53.88g/100ml) room temperature immersion, health preserving 1hr, 120 DEG C of dry 2hr, temperature programming 550 DEG C roasting
Burning 5hr, prepare catalyst III, physico-chemical property is shown in Table 2.
Comparative example 1:
Take abroad the most industrialized typical in oil type catalyst make comparisons agent IV.This catalyst is
The most industrialized middle fraction oil type hydrocracking catalyst of one, the molecular sieve of use is modified
Y, physico-chemical property is shown in Table 2.
Table 2 catalyst physico-chemical property
| Sample number into spectrum | Ⅰ | Ⅱ | Ⅲ | Ⅳ |
| Catalyst forms, % | ||||
| Macropore amorphous silicon aluminium | 41.9 | 38.6 | 39.6 | / |
| Macroporous aluminium oxide | 7.0 | 3.5 | 10.4 | / |
| Little porous aluminum oxide | 14.0 | 17.5 | 13.9 | / |
| β zeolite | 7.0 | 10.5 | 5.6 | / |
| WO3 | 23.1 | 22.6 | 22.9 | 23.3 |
| NiO | 7.0 | 7.3 | 7.6 | 7.1 |
| Specific surface area, m2/g | 226 | 248 | 241 | 192 |
| Pore volume, ml/g | 0.33 | 0.32 | 0.32 | 0.33 |
Embodiment 7,8,9 describes the inventive method and heavy hydrocarbon oil is hydrocracked result.
Embodiment 7:
Catalyst I in Example, uses single hop series connection once by technique, solid at 200ml
Evaluate on fixed bed hydrocracking unit, appreciation condition: reaction pressure 13.5MPa, hydrogen to oil volume ratio
800:1, volume space velocity 1.5hr-1, control 370 DEG C of tail oil yields of ＞ and be about 30%.Evaluation raw material is
Grand celebration paraffinic base VGO, raw material oil properties is listed in table 2, and evaluation result is listed in table 3.
Embodiment 8:
Catalyst II in Example, uses single hop series connection once by technique, solid at 200ml
Evaluating on fixed bed hydrocracking unit, appreciation condition is with embodiment 7, and evaluating raw material is grand celebration paraffinic base
VGO, raw material oil properties is listed in table 2, and evaluation result is listed in table 3.
Embodiment 9:
Catalyst III in Example, uses single hop series connection once by technique, solid at 200ml
Evaluating on fixed bed hydrocracking unit, appreciation condition is with embodiment 7, and evaluating raw material is grand celebration paraffinic base
VGO, raw material oil properties is listed in table 2, and evaluation result is listed in table 3.
Comparative example 2 describes contrast medium and heavy hydrocarbon oil is hydrocracked result.
Comparative example 2:
Take the catalyst IV in comparative example 1, use single hop series connection once to pass through technique, at 200ml
Evaluating on fixed bed hydrogenation cracking unit, appreciation condition is with embodiment 7, and evaluating raw material is grand celebration paraffin
Base VGO, raw material oil properties is listed in table 2, and evaluation result is listed in table 3.
Raw oil character evaluated by table 3
| Project | Raw oil |
| Boiling range, DEG C | |
| HK/5% | 231/300 |
| 10%/30% | 340/377 |
| 50%/70% | 404/444 |
| 90%/KK | 480/516 |
| Density (20 DEG C), g/cm3 | 0.8618 |
| BMCI value | 26.0 |
| Condensation point, DEG C | 36.5 |
| Sulfur content, μ g/g | 957.9 |
| Nitrogen content, μ g/g | 1096.6 |
| Carbon residue, % | 0.158 |
| Race forms, % | |
| Alkane | 42.1 |
| Cycloalkane | 38.8 |
| Aromatic hydrocarbons | 19.1 |
The 200ml of table 3 catalyst is hydrocracked Evaluation results
Claims (1)
1. the method that a heavy hydrocarbon oil is hydrocracked, it is characterised in that: heavy hydrocarbon oil is volume space velocity 0.5hr when reaction temperature 300 DEG C～500 DEG C, hydrogen dividing potential drop 8MPa～20MPa, hydrogen to oil volume ratio 500:1～2000:1, liquid-1～3.0hr-1Under process conditions, carry out heavy hydrocarbon oil catalytic hydrocracking；
Hydrocracking catalyst is count by weight percentage: β zeolite 2%～20%；Refractory inorganic oxides 20%～70%；VI B family metal oxide 10%～25%；VIII family metal oxide 3%～10%；
β zeolite preparation method is as follows:
Adding master module agent tetraethyl ammonium halide in sodium hydroxide solution, molecular formula is TEA+X-Wherein one or both mixture in X=Cl, Br, are stirring evenly and then adding into aluminum source, stirring and dissolving to transparent addition silicon source, continue stirring 1h～4h, by gained mixture low temperature maturation 2h～16h at 40 DEG C～100 DEG C, gained initial reaction mixture is placed on the multiple sieve plate in reactor, bottom reactor, adds water and the mixture of low carbon number organic amine auxiliary template agent, heat up, crystallization 24h～60h at 130 DEG C～160 DEG C, products therefrom, through filtering, washing and be dried, obtains β zeolite；
The mol ratio of synthetic system material is: SiO2/AlO3=30～300, TEA+/SiO2=0.05～0.30, Na2O/SiO2=0.15～0.80, H2O/SiO2=7～15；
The mol ratio of reactor bottoms material is H2O/SiO2=0.5～2.0, R/SiO2=0.08～0.18, R are low carbon number organic amine auxiliary template agent；The described mixture that master module agent tetraethyl ammonium halide is a kind of or its arbitrary proportion in tetraethylammonium bromide, tetraethylammonium chloride；The described mixture that auxiliary template agent is triethylamine, diethylamine or its arbitrary proportion；
The SiO of described β zeolite2/Al2O3Mol ratio is 30～200, and sodium oxide content is ＜ 0.5%, and specific surface area is 300m2/ g～800m2/ g, pore volume is 0.2ml/g～0.45ml/g；Described hydro carbons heavy oil is coker gas oil, vacuum gas oil (VGO), AGO (atmospheric gas oil), dewaxed oil and compound thereof, boiling range scope at 200 DEG C～580 DEG C, nitrogen content ≯ 2000 μ g/g, sulfur content 0.05%～3%, carbon residue ≯ 0.7%, asphalitine ＜ 0.02%, tenor ≯ 3 μ g/g.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249270A (en) * | 1998-09-25 | 2000-04-05 | 北京燕山石油化工公司研究院 | Process for synthesizing beta-zeolite |
| CN1508231A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Recycle-cracking hydrocracking process |
| JP2006257154A (en) * | 2005-03-15 | 2006-09-28 | Nippon Oil Corp | Method for producing low aromatic solvent |
| CN102909060A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Preparation method for hydrocracking catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249270A (en) * | 1998-09-25 | 2000-04-05 | 北京燕山石油化工公司研究院 | Process for synthesizing beta-zeolite |
| CN1508231A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Recycle-cracking hydrocracking process |
| JP2006257154A (en) * | 2005-03-15 | 2006-09-28 | Nippon Oil Corp | Method for producing low aromatic solvent |
| CN102909060A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Preparation method for hydrocracking catalyst |
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