CN104826653B - A kind of method for preparing hydrocracking catalyst - Google Patents
A kind of method for preparing hydrocracking catalyst Download PDFInfo
- Publication number
- CN104826653B CN104826653B CN201410045554.3A CN201410045554A CN104826653B CN 104826653 B CN104826653 B CN 104826653B CN 201410045554 A CN201410045554 A CN 201410045554A CN 104826653 B CN104826653 B CN 104826653B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- accordance
- hours
- crystal grain
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of method for preparing hydrocracking catalyst.The method includes:By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and with binding agent mixing, molding made by aluminium oxide, then it is dried and roasting, makes catalyst carrier, then load hydrogenation active metals component, drying and roasting, make catalyst;Wherein using silica alumina ratio is higher, degree of crystallinity is high, the NaY type Molecular sieve raw materials of good stability, sequentially pass through ammonium exchange, first time hydrothermal treatment consists, containing alkaline solution treatment, second hydrothermal treatment consists and after being processed with the mixed solution of ammonium salt with acid, resulting small crystal grain Y-shaped molecular sieve is obtaining higher SiO2/A12O3While mol ratio, the ratio shared by secondary pore is higher, and maintains the stability of Y type molecular sieve, and molecular sieve has higher specific surface area and higher degree of crystallinity.Hydrocracking catalyst of the present invention suitably as senior middle school's oil hydrocracking catalyst, with good activity, middle distillates oil selectivity and excellent product property.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst, more specifically a kind of containing small-grain Y-type point
The preparation method of the hydrocracking catalyst of son sieve.
Background technology
As international refined products market is continuously increased to the demand of intermediate oil, in needing more to obtain from mink cell focus
Between distillate, and one of important means of hydrocracking process exactly light materialization of heavy oil.As there is the technique raw material to adapt to
Property strong, good product quality, adjust flexible operation, midbarrel product yield is high, the features such as product structure is flexible so that hydrogenation splits
The status of chemical industry skill becomes more and more important, particular for China be faced with present petroleum resources shortage, environmental requirement it is increasingly tight
The problems such as lattice and oil product structure are not suitable with market, the application of hydrocracking technology will become raising petroleum product-quality,
Reduce environmental pollution, increase the effective technology measure of market adaptability to changes, it has also become the of paramount importance technique dress in modernization refinery
Put.Exactly these factors promote high selectivity to middle distillates hydrocracking technology and rapidly develop, and hydrocracking catalyst is
The key of the technology.
Carrier is the important component part of catalyst, not only provides dispersion place for metal active constituent, while carrier sheet
Body also assists in reaction, cooperates with and complete whole catalytic reaction together with other active components, and hydrocracking catalyst is a kind of pair of work(
Energy catalyst, it contains acidic components and hydrogenation component simultaneously.Hydrogenation activity is selected generally from VI B races in the periodic table of elements and
VIII race's metal is provided;And its acidic components is mainly provided by zeolite and inorganic oxide, major part is with aluminium oxide or without fixed
Shape sial is carrier, is equipped with a certain amount of molecular sieve.And the key component that cracking is played in such catalyst is usually Y molecules
Sieve, the quality of Y molecular sieve performance directly affect the performance and product quality of catalyst.
Y type molecular sieve is at present universal in residual oil cracking field cracking active component, and crystal grain is generally
1000nm or so, its crystal grain are larger, and duct is relatively long, and diffusional resistance is big, and macromole is difficult to be reacted into inside duct,
After reaction, product is also more difficult diffuses out, so the selectivity of its cracking activity and purpose product receives restriction.With conventional Y types
Molecular sieve is compared, and small crystal grain Y-shaped molecular sieve has bigger external surface area and more outer surface active center, is conducive to improving big point
Sub- hydrocarbon cracking capability, thus with more superior catalytic perfomance.Meanwhile, reducing Y type molecular sieve crystallite dimension can be with
Improve inner surface active sites utilization rate.In general, diffusion of the reactant molecule in molecular sieve endoporus duct is referred to as transgranular expansion
Dissipate.Molecular sieve inner surface is made all to be used for catalyzed conversion, it is necessary to make micropore diffusion speed be more than endoporus catalyzed conversion
Speed.It is the best way to shorten the evolving path.The effective way that micropore diffusion is limited is overcome to be to reduce zeolite crystal
Size.This can not only increase the external surface area of zeolite crystal, and while shorten diffusion length.EP0204236 is to little
Crystal NaY molecular sieve and big crystal grain NaY molecular sieve are compared, and are as a result shown, the former has higher to RFCC
Active and preferable selectivity.
Small crystal grain NaY molecular sieve is that do not possess acidity, and needs are modified process, to meet the performance of Cracking catalyst
Require.CN1382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, and the method is to be dried gas with Silicon chloride.
Body and fine grain NaY zeolitic contact, obtain after washing, due to the heat and hydrothermal stability of its raw material itself it is just poor, while
The method is by the way of gas phase dealumination complement silicon to process molecular sieve, and this causes the heat and hydrothermal stability of product worse, activity
It is low.Especially poor to heat stability and hydrothermal stability fine grain NaY zeolite, the sial framing structure stability in zeolite
It is poor, the removing of framework aluminum is easily caused in modifying process, while also some framework silicon causes portion also with removing
Skeleton is divided the phenomenon caved in occur so that the crystallization reservation degree of product is relatively low, and the activity of zeolite is not high.
CN200910188140.5 discloses a kind of hydrocracking catalyst and preparation method thereof.The catalyst includes hydrogenation
The carrier of active metal component and small-grain Y molecular sieve, amorphous silica-alumina and aluminium oxide composition, wherein the small-grain Y-type point
Son sieve be using hydrothermal treatment consists after small crystal grain Y-shaped molecular sieve.During raw materials used small crystal grain NaY molecular sieve is CN101722023A
Prepared by disclosed method, i.e. SiO2/Al2O3Mol ratio be 4.0~6.0, mean diameter in 100~700nm, after passing sequentially through
The mixed aqueous solution of continuous modified i.e. ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydrothermal treatment consists, aluminium salt and acid is processed, and obtains little crystalline substance
Grain Y molecular sieve.In the method, after needing first raw material is processed with ammonium hexafluorosilicate dealumination complement silicon, then the process such as hydrothermal treatment consists is carried out,
The framing structure that molecular sieve could so be reduced is caved in, and improves the crystallization reservation degree of molecular sieve, but the method due to first with six
After the process of ammonium fluosilicate dealumination complement silicon, due to there is sial isomorphous substitution, molecular sieve silica constructed of aluminium is than more complete, then enters water-filling
Heat treatment, the secondary pore of formation are few, and secondary pore proportion is low, and used as catalyst molecule screen banks point, middle oil yield is low.
In preparation process, silicon and aluminum are easy to run off existing method fine grain NaY type molecular sieve, and silicon utilization rate is low, and silicon,
Aluminum distributing inhomogeneity, easily occurs reuniting, therefore existing method still cannot prepare silica alumina ratio height, and heat stability and hydro-thermal are steady
Qualitative and good fine grain NaY type molecular sieve.Through successive modified, it is impossible to obtain structural integrity, degree of crystallinity is high and has more
The small crystal grain Y-shaped molecular sieve of secondary pore, used as the cracking component of catalyst, middle oil yield is low.
The content of the invention
For weak point of the prior art, the invention provides a kind of preparation of the good hydrogenation catalyst of catalytic performance
Method.A kind of dealumination depth is big, degree of crystallinity holding is good, the little crystalline substance that secondary pore is flourishing using providing for the hydrocracking catalyst
Used as acidic components, prepared hydrocracking catalyst has a higher activity to grain Y type molecular sieve, middle distillates oil selectivity and excellent
Product property.
The preparation method of hydrocracking catalyst of the present invention, comprises the steps:
By small-grain Y molecular sieve, amorphous silica-alumina and with binding agent mechanical mixture, molding, Ran Hougan made by aluminium oxide
Dry and roasting, makes catalyst carrier;Supported active metals component, drying and roasting in the catalyst carrier of gained, make
Catalyst;
Wherein described small-grain Y molecular sieve, including following preparation process:
(1) preparation of fine grain NaY type molecular sieve;
(2) by step(1)Fine grain NaY type molecular sieve be prepared into Na2Little crystal grain NH of O content≤1.5wt%4NaY;
(3) with little crystal grain NH4NaY is raw material, carries out first time hydrothermal treatment consists;
(4) molecular sieve for obtaining step (3) is with containing alkaline solution treatment;
(5) molecular sieve that step (4) is obtained is carried out into second hydrothermal treatment consists;
(6) the molecular sieve acid for obtaining step (5) and the mixed solution of ammonium salt are processed, and Jing is washed and is dried to obtain little crystalline substance
Grain Y type molecular sieve.
Step(1)Described in small crystal grain NaY molecular sieve, its property is as follows: SiO2/Al2O3Mol ratio is more than 6.0 and not
Higher than 9.0, preferably 6.5~9.0, more preferably 7.0~8.0, average grain diameter be 200~700nm, preferably 300~
500nm;Specific surface area is 800~1000 m2/ g, preferably 850~950 m2/ g, 0.30/~0.45mL/g of pore volume are relative to tie
Brilliant degree is 90%~130%, and cell parameter is 2.460~2.470nm, the relative crystallinity Jing after roasting in 650 DEG C of air 3 hours
It is for more than 90%, generally 90%~110%, preferably 90% ~ 105%, relative Jing after 700 DEG C of water vapour hydrothermal treatment consists 2 hours
Degree of crystallinity is more than 90%, generally 90%~110%, preferably 90% ~ 105%.
In the inventive method, in step (1), the preparation method of fine grain NaY type molecular sieve is as follows:
I, preparation directed agents:Silicon source, silicon source, alkali source and water are fed intake according to following proportioning:(6~30) Na2O:Al2O3:(6
~30) SiO2:(100~460) H2Mixture, after stirring, at 0~20 DEG C is stirred ageing and is obtained for 0.5~24 hour by O
Directed agents;
II, using preparing amorphous silicon alumnium using carbonization predecessor, the weight with the butt of amorphous silica-alumina predecessor is as base
Standard, the content that silicon is counted with silicon dioxide as 40wt%~75wt%, preferably 55 wt%~70wt%;Its preparation process includes:
A, respectively preparation sodium aluminate solution and sodium silicate solution;
The part sodium silicate solution for adding step a to prepare in b, the sodium aluminate solution prepared to step a, then passes to CO2
Gas, controlling reaction temperature are 10 ~ 40 DEG C, and preferably 15~35 DEG C, the pH value for controlling cemented into bundles is 8 ~ 11;Wherein when being passed through
CO2Gas flow accounts for the 60% ~ 100% of total intake, when preferably 80% ~ 100%, adds remainder sodium silicate solution, wherein
In step b, remainder sodium silicate solution accounts for step b addition sodium silicate solution total amount in terms of silicon dioxide in terms of silicon dioxide
5wt% ~ 85wt%, preferably 30wt% ~ 70wt%;
C, at the control temperature and pH value of step b, said mixture ventilation stablize 10 ~ 30 minutes;
III, prepare silica-alumina gel
By (0.5~6) Na2O:Al2O3:(8~15) SiO2:(100~460) H2Total molar ratio of O, at 0~40 DEG C
To step under conditions of quick stirring(2)Water, silicon source, directed agents and alkali source are added in the amorphous silica-alumina predecessor of gained, and
Control ph is 9.5 ~ 12.0, and uniform stirring obtains silica-alumina gel;Wherein directed agents addition accounts for the 1% of silica-alumina gel weight
~20%,
Two step dynamic crystallizations of reactant mixture Jing obtained by IV, step III, then Jing filtrations, washing, are dried, obtain little crystalline substance
Grain NaY molecular sieve.
In the present invention, in step I and III, silicon source, alkali source are respectively selected from sodium silicate and sodium hydroxide.In step I, silicon source
Selected from sodium metaaluminate.
In step II, the concentration of the sodium aluminate solution used by step a is preferably 15~55g Al2O3/ L, sodium silicate solution
Concentration be 50~150 gSiO2/ L, CO used by step b2The concentration of gas is 30v% ~ 60v%.
In step III, 0~40 DEG C of controlling reaction temperature, preferably 10 ~ 30 DEG C, pH value 9.5~12.0, preferable ph 10~
11。
In step IV, the reactant mixture of gained carries out crystallization using two step dynamic crystallizations, and the wherein first step enters Mobile state
The condition of crystallization is as follows:At 50~90 DEG C, crystallization time is 0.5~18 hour to temperature control;Second step carries out dynamic crystallization
Condition is as follows:At 80~140 DEG C, crystallization time is 3~10 hours to temperature control, and after the completion of crystallization, then Jing is filtered, washs, done
It is dry, product is obtained.Two step dynamic crystallization conditions are preferably as follows:The first step:Temperature control at 60~80 DEG C, crystallization time is 1~
10 hours;Second step:At 80~120 DEG C, crystallization time is 5~10 hours to temperature control.
Step(2)In, with fine grain NaY type molecular sieve as raw material, with containing H+Ammonium salt aqueous solution at 70~120 DEG C,
Exchange 0.5~3.0 hour at preferably 80~100 DEG C.Wherein described ammonium salt such as ammonium chloride, ammonium carbonate, ammonium nitrate, sulphuric acid
One or more in ammonium, ammonium acetate, ammonium oxalate, ammonium citrate etc..H is provided in aqueous solution+Acid can be hydrochloric acid, carbonic acid,
One or more in nitric acid, sulphuric acid.In aqueous solution, H+Concentration be 0.005~0.5mol/L, NH4 +Concentration be 0.5~
5.0mol/L.Y type molecular sieve exchange serosity in concentration be 0.05~0.5g/mL, repeated exchanged l~5 time, filter off mother solution,
Washing, is dried prepared Na2O content is in below 1.5wt%.
Step(3)Described first time hydrothermal treatment consists temperature be 500 DEG C~700 DEG C, water vapor pressure be 0.01~
1.0MPa, process time are 1.0~10.0 hours.
Step(4)By step(3)The molecular sieve for obtaining is mixed homogeneously with the aqueous solution beating of alkali, and maintains 60~120 DEG C
Temperature conditionss under 1~4h of stir process, filter, washing.Alkali is selected from the mixture of NaOH, KOH or NaOH and KOH.The water of alkali
The concentration of solution is generally 0.1~3.0 mol/L, and in serosity, the concentration of molecular sieve is 0.05~1.0g/mL.
Step(5)Second described hydrothermal treatment consists temperature is 500~800 DEG C, and water vapor pressure is 0.01~1.0MPa,
Process time is 1.0~10.0 hours, and second hydrothermal treatment consists temperature is identical greater than or equal to first time hydrothermal treatment consists temperature.
Step(6)In, by the molecular sieve after hydrothermal treatment consists with acid and containing NH4 +Salt composition mixed solution contact, exchange
Na in molecular sieve+With the part non-framework aluminum in removing molecular sieve, acid therein can be hydrochloric acid, carbonic acid, nitric acid, in sulphuric acid
One or more, containing NH4 +Salt be one or more in the ammonium salt containing above acid group;H in mixed solution+Concentration be
0.05~0.6mol/L, NH4 +Concentration be 0.5~3.0mol/L, exchange temperature be 70~120 DEG C, exchange serosity in molecular sieve
Concentration be 0.1~0.5g/mL, swap time be 0.5~3.0 hour, exchange step may be repeated 1~4 time.Then remove
Mother solution, washes with water, is dried.
Detailed process prepared by carrier of hydrocracking catalyst of the present invention is:By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina
Mix with binding agent, extruded moulding, be then dried 3~10 hours and at 500 DEG C~600 DEG C at a temperature of 80 DEG C~150 DEG C
Roasting 3~6 hours, is prepared into carrier.
Adhesive therefor of the present invention is made up of little porous aluminum oxide and mineral acid and/or organic acid.Aperture oxidation used
Aluminum pore volume is 0.3~0.5 mL/g, and specific surface area is 200~400m2/g。
In catalyst carrier of the present invention, mixing amorphous silica-alumina used with small-grain Y molecular sieve and binding agent can be by altogether
Prepared by the sedimentation method or grafting copolymerization process, prepare by conventional method in document.SiO in obtained amorphous silica-alumina2Weight
Content is 20%~60%, preferably 25%~40%, and the pore volume of amorphous silica-alumina is 0.6~1.1 mL/g, preferably 0.8~
1.0 mL/g, specific surface area are 300~500 m2/ g, preferably 350~500 m2/g。
Catalyst of the present invention can carry out molding according to actual needs, and shape can be cylindrical bars, Herba Trifolii Pratentis etc..Catalyst into
During type, shaping assistant, such as peptization acid, extrusion aid etc. can also be added.Catalyst carrier of the present invention is using conventional method
It is dried and roasting, it is specific as follows:It is dried 3~10 hours at a temperature of 80 DEG C~150 DEG C and roasts at 500 DEG C~600 DEG C
Burn 3~6 hours.
The load of catalyst activity metal of the present invention, can adopt conventional carrying method in prior art, preferred infusion process,
Can be saturation leaching, excessive leaching or complexation leaching, i.e., with the solution impregnated catalyst carrier containing required active component, after dipping
Carrier is dried l~12 hour at 100 DEG C~150 DEG C, then in 450 DEG C~550 DEG C roastings 3~6 hours, final catalysis is obtained
Agent.
Hydrocracking catalyst of the present invention, including hydrogenation active metals component and by small-grain Y molecular sieve, with oxidation aluminum
Into binding agent and amorphous silica-alumina composition carrier, wherein described small-grain Y molecular sieve, its property is as follows:SiO2/ A12O3
Mol ratio be 40~120, average grain diameter be 200~700nm, preferably 300~500nm, relative crystallinity >=95%, structure cell
2.425~2.440nm of constant, 900~1200m of specific surface area2/ g, 0.5/~0.80mL/g of pore volume, 1.7~10nm's are secondary
Pore volume shared by hole is total pore volume more than 60%.
Hydrocracking catalyst property of the present invention is as follows:Specific surface area is 300~500 m2/ g, pore volume are 0.35~0.60
ML/g. the pore volume of 4 ~ 10nm of aperture accounts for the 60%~95% of total pore volume, and preferably 70%~90%.
The hydrocracking catalyst of the present invention, described hydrogenation active metals are the metal of vib and/or the VIIIth race,
Vib metals are preferably molybdenum and/or tungsten, and the metal of the VIIIth race is preferably cobalt and/or nickel.On the basis of the weight of catalyst,
Vib metals(In terms of oxide)Content be 10wt%~30wt% and group VIII metal(In terms of oxide)Content be
4wt%~10wt%, the content of carrier is 61wt%~86wt%.
Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, its composition includes:Small-grain Y-type molecule
The content of sieve is 5wt%~40wt%, and it is 10 that the content of amorphous silica-alumina is 20 wt%~65 wt%, the content of aluminium oxide
Wt%~40 wt%.
Hydrocracking catalyst of the present invention is used for hydrocracking process, is suitable for treatment of heavy hydrocarbon material, it is adaptable to this law
Heavy charge scope it is very wide, they include vacuum gas oil (VGO), and coker gas oil, deasphalted oil, thermal cracking gas oil, catalysis split
Change the various hydrocarbon-type oils such as gas oil, catalytic cracking recycle oil, can also be used in mixed way, raw material usually contains 300~600 DEG C of boiling point
Hydro carbons, nitrogen content can be in 50~2500mg/g.
The hydrocracking catalyst of the present invention is particularly well-suited to single hop once by, in method for hydrogen cracking, operating condition is such as
Under:350~420 DEG C of reaction temperature, more preferably 360~390 DEG C, 6~20MPa of hydrogen dividing potential drop, more preferably 9~15MPa, hydrogen oil volume
Than 500~2000:1, more preferably 800~1500:1,0.5~1.8 h of volume space velocity during liquid-1, more preferably 0.8~1.5h-1。
Due to the small-grain Y molecular sieve that catalyst of the present invention is adopted, the silica alumina ratio of its NaY type Molecular sieve raw material is higher, knot
Brilliant degree is high, good stability, so in follow-up modification process, the crystal structure that saboteur does not sieve, so as to not affect most
The stability of whole molecular sieve.The present invention is by hydrothermal treatment consists twice, and coordinates alkali process process twice between hydrothermal treatment consists, i.e.,
Preferable dealumination depth is reached, and has preferably maintained the rock-steady structure of molecular sieve, while substantial amounts of secondary pore is generated, no
Only promote the performance of hydrogenation activity, and be conducive to the diffusion of product, hold charcoal ability and also greatly enhance, reduce excessively
Cracking and the occurrence probability of second pyrolysises, have activity, middle distillates oil selectivity and excellent product well so as to make catalyst
Property.
In addition adopt small crystal grain molecular sieve for Cracking Component in carrier of the present invention, with bigger external surface area and it is more outward
Active sites, are conducive to improving macromole hydrocarbon cracking capability, can make being hydrocracked for active component by this molecular sieve
The activity increase of catalyst, while the performance of catalyst hydrogenation performance can be advantageously promoted.
Specific embodiment
In order to the present invention is better described, the present invention is further illustrated with reference to embodiment and comparative example.But this
Bright scope is not limited solely to the scope of these embodiments.Analysis method of the present invention:Specific surface area, pore volume adopt low temperature liquid nitrogen physics
Absorption method, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio to adopt chemical method, and the crystal grain of molecular sieve is big
It is little to be determined by the way of SEM (scanning electron microscope).Wt% is mass fraction.
Embodiment 1
The present embodiment is preparing raw material fine grain NaY type molecular sieve
The preparation of NY-1
(1)The preparation of directed agents:Take 10 g sodium hydrate solids to be dissolved in 80g water, add sodium metaaluminate 2g (Al2O3Contain
Measure as 45wt%, Na2O content is 41wt%), then add 36g waterglass (SiO2Content is 28wt%, Na2O content is 8
Wt%), in 15 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.
(2)The preparation of amorphous silica-alumina predecessor
Solid sodium aluminate is configured to into concentration for 40gAl2O3/ L sodium aluminate working solutions, take containing SiO2The silicic acid of 28wt%
Sodium solution, then concentration is diluted to for 100g SiO2/ L sodium silicate working solutions.Take 1L sodium aluminate working solutions and be placed in plastic cans
In, 0.2L sodium silicate working solutions are subsequently adding, 20 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%2Gas, works as pH value
Stop logical CO when reaching 10.02, 0.4L sodium silicate working solutions are added, then ventilation stablizes 20 minutes.
(3)The preparation of gel
In step(2)100g SiO are added in resulting serosity2/ L sodium silicate working solution 1.5L and step(1)Prepare
Directed agents 120g, the pH value of gel is 12, and 20 DEG C of controlling reaction temperature, uniform stirring 30 minutes staticize 2 hours.
(4)Crystallization
By step(2)Resulting gel is poured in stainless steel cauldron, is stirred crystallization 4 hours at 70 DEG C, is then heated up
To 100 DEG C, stirring crystallization 8 hours, then filter, washing, dry NaY molecular sieve product NY-1, product property is shown in Table 1.
The preparation of NY-2
(1)The preparation of directed agents:Take 8 g sodium hydrate solids to be dissolved in 80g water, add 2.5 g (Al of sodium metaaluminate2O3
Content is 45wt%, Na2O content is 41wt%).Then 40g waterglass (SiO are added2Content is 28wt%, Na2O content is 8
Wt%), in 18 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.
(2)The preparation of amorphous silica-alumina predecessor
Solid sodium aluminate is configured to into concentration for 30gAl2O3/ L sodium aluminate working solutions, take containing SiO2The silicic acid of 28wt%
Sodium solution, then concentration is diluted to for 70g SiO2/ L sodium silicate working solutions.Take 1L sodium aluminate working solutions to be placed in plastic cans,
0.4L sodium silicate working solutions are subsequently adding, 18 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%2Gas, when pH value reaches
To the logical CO of stopping when 10.22, 0.6L sodium silicate working solutions are added, then ventilation stablizes 20 minutes.
(3)The preparation of gel
In step(2)70g SiO are added in resulting serosity2/ L sodium silicate working solution 1.5L and step(1)Prepare
Directed agents 100g, the pH value of gel is 11.5, and 15 DEG C of controlling reaction temperature, uniform stirring 30 minutes staticize 2.5 hours.
(4)Crystallization
By step(2)Resulting gel is poured in stainless steel cauldron, is stirred crystallization 5 hours at 75 DEG C, is then heated up
To 110 DEG C, stirring crystallization 7 hours, then filter, washing, dry NaY molecular sieve product NY-2, product property is shown in Table 1.
Embodiment 2
Ammonium exchange is carried out to raw material fine grain NaY type molecular sieve NY-1 first.Prepare containing NH4 +And H+Concentration be respectively
10 liters of the solution (ammonium chloride and hydrochloric acid mixed solution) of 1.0mol/L and 0.02mol/L.Weigh small crystal grain NaY molecular sieve 1000
Gram, it is added in above-mentioned mixed solution, speed of agitator is 300rpm, the constant temperature stirring l hours at 90 DEG C, then filtering molecular
Sieve, and sample is stayed, analyze Na2O content;Repeat aforesaid operations, the Na in molecular sieve2O content reaches 1.5wt%, is done
Sample number into spectrum after dry is NNY-1.
Embodiment 3
Ammonium exchange is carried out to raw material fine grain NaY type molecular sieve NY-2 first.Prepare containing NH4 +And H+Concentration be respectively
0.8.0mol/L with 10 liters of the solution of 0.01mol/L (ammonium nitrate and nitric acid mixed solution).Weigh small crystal grain NaY molecular sieve
1000 grams, it is added in above-mentioned mixed solution, speed of agitator is 300rpm, then the constant temperature stirring l hours at 95 DEG C filter and divide
Son sieve, and sample is stayed, analyze Na2O content;Repeat aforesaid operations, the Na in molecular sieve2O content reaches 1.5wt%, obtains
Dried sample number into spectrum is NNY-2.
Embodiment 4
Take 100 grams of NNY-1 type molecular sieves to be placed in heat-treatment furnace, control 400 DEG C/h of heating rate, by temperature liter
To 650 DEG C, while the steam partial pressure 0.08MPa of the system of maintenance, is processed 2 hours, sample is taken out in cooling;By the molecule for obtaining
Sieve is that the beating of 0.5mol/L KOH solutions is mixed homogeneously with 600mL concentration, and maintains stir process 2h under 90 DEG C of temperature conditionss,
Filter, be washed to the close neutrality of solution;Wet cake is placed in heat-treatment furnace, temperature is risen to into 700 DEG C, and control water in stove and steamed
Steam pressure is 0.1MPa, and constant temperature 2 hours, cooling take out sample;Final sample is with containing NH4 +And H+Concentration be respectively 1.0mol/
The mixed solution 600mL of L ammonium nitrates and 0.15mol/L nitric acid is contacted with sample and is stirred, and is processed 3 hours, mistake at 100 DEG C
Filter, washing are dried, and obtain modified small-grain Y -1.The physico-chemical property of Y-1 is shown in Table 1.
Embodiment 5
Take 100 grams of NNY-2 type molecular sieves to be placed in heat-treatment furnace, control 450 DEG C/h of heating rate, by temperature liter
To 650 DEG C, while the steam partial pressure 0.15MPa of the system of maintenance, is processed 2 hours, sample is taken out in cooling;By the molecule for obtaining
Sieve contains H with 500mL+KOH the and NaOH mixed solutions beating mix homogeneously of concentration 0.8mol/L, and maintain 100 DEG C of temperature strip
Stir process 2h under part, filters, is washed to the close neutrality of solution;Wet cake is placed in heat-treatment furnace, temperature is risen to into 650
DEG C, and to control in stove water vapor pressure be 0.15MPa, constant temperature 2 hours, cooling take out sample;Final sample is with containing NH4 +And H+
Concentration be respectively 1.5mol/L and 0.3mol/L solution (ammonium nitrate and nitric acid mixed solution) 600mL contact with sample and stir
Mix, process 3 hours at 95 DEG C, filter, washing is dried, obtain modified small-grain Y -2.The physico-chemical property of Y-2 is shown in Table 1.
Embodiment 6
By 30 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide
You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then
In 550 DEG C of roastings 4 hours, carrier TCAT-1 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 7
By 40 grams of Y-2 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide
You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then
In 550 DEG C of roastings 4 hours, carrier TCAT-2 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CAT-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 1
1st, fine grain NaY is prepared with reference to CN101722023A.
In this comparative example, feedstock property used is as follows:Low alkali sodium metaaluminate:Na2O content 120g/L, Al2O3Content
40g/L;Waterglass:SiO2Content 250g/L;Aluminum sulfate:Al2O3Content 90g/L.
(1) preparation of directed agents:The preparation of directed agents is with NY-1 in embodiment 1.
(2) preparation of gel:Temperature is 8 DEG C, under stirring condition, sequentially adds 59.4mL sulfur in the waterglass of 208mL
Sour aluminum, the low sodium metaaluminate of 62.7mL and 42.2mL directed agents, then constant temperature constant speed stirring 1.5 hours, then by the conjunction for obtaining
Into liquid static aging 8 hours at the temperature disclosed above, gel is obtained.
(3) crystallization:Under agitation, the gel in synthesis reactor is raised to into 50 DEG C in 20 minutes, constant temperature stirring crystallization 7
Hour;After low temperature crystallized end, the temperature in synthesis reactor is brought up to into 120 DEG C in 20 minutes, then constant temperature is stirred 6 hours.
Jing is filtered, washs and is dried, and obtains product little crystal grain CNY-l.
2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve CNY-1, treatment conditions obtain dried with embodiment 2
Sample number into spectrum is CNNY-1.
3rd, subsequent treatment is carried out to CNNY-1, processing mode and condition obtain Reference Product CY-1 with embodiment 4.CY-1
Physico-chemical property be shown in Table 1.
4th, by 30 grams of CY-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide
You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then
In 550 DEG C of roastings 4 hours, carrier TCCAT-1 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 2
1st, fine grain NaY is prepared with reference to CN1785807A.
The preparation of directed agents:The preparation of directed agents is with NY-1 in embodiment 1.
14.21g water is positioned in beaker, it is 60 DEG C to control temperature of liquid in beaker, quick stirring is lower to be added simultaneously
The A1 of 12.79g50wt%2(SO4)3) solution and 31.91g waterglass.After stirring, above-mentioned directed agents 1.90g, gel are added
PH value be 12.5, after stirring, be loaded in stainless steel cauldron, stir crystallization 6 hours at 60 DEG C, then heat to
100 DEG C of static crystallizations 60 hours, then filter, washing, dry CNY-2 molecular sieves.
2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve CNY-2, treatment conditions obtain dried with embodiment 2
Sample number into spectrum is CNNY-2.
3rd, subsequent treatment is carried out to CNNY-2, processing mode and condition obtain Reference Product CY-2 with embodiment 4.CY-2
Physico-chemical property be shown in Table 1.
4th, by 30 grams of CY-2 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide
You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then
In 550 DEG C of roastings 4 hours, carrier TCCAT-2 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 3
1st, prepared by fine grain NaY
(1)The preparation of directed agents:The preparation of directed agents is with NY-1 in embodiment 1.
(2)The preparation of amorphous silica-alumina predecessor.
Solid sodium aluminate is configured to into concentration for 40gAl2O3/ L sodium aluminate working solutions, take containing SiO2The silicic acid of 28wt%
Sodium solution, then concentration is diluted to for 100g SiO2/ L sodium silicate working solutions.Take 1L sodium aluminate working solutions and be placed in plastic cans
In, 0.6L sodium silicate working solutions are subsequently adding, 20 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%2Gas, works as pH value
Stop logical CO when reaching 10.02, then divulge information and stablize 20 minutes.
(3)The preparation of gel is with embodiment 1.
(4)Crystallization obtains products C NY-3 with embodiment 1, and product property is shown in Table 1.
2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve CNY-3, treatment conditions obtain dried with embodiment 2
Sample number into spectrum is CNNY-3.
3rd, subsequent treatment is carried out to CNNY-3, processing mode and condition obtain Reference Product CY-3 with embodiment 4.CY-3
Physico-chemical property be shown in Table 1.
By 40 grams of CY-3 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide
You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then
In 550 DEG C of roastings 4 hours, carrier TCCAT-3 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-3 is obtained, carrier and corresponding catalyst property are shown in Table 2.
The property of 1 Y type molecular sieve of table
Production code member | NY-1 | NY-2 | Y-1 | Y-2 | CY-1 | CY-2 | CY-3 |
Feed intake SiO2/Al2O3Mol ratio | 9.1 | 10.1 | |||||
SiO2/Al2O3Mol ratio | 7.5 | 8.4 | 115 | 89 | 50 | 25 | 28 |
Specific surface area, m2/g | 916 | 898 | 1140 | 1090 | 940 | 801 | 815 |
Pore volume, mL/g | 0.39 | 0.38 | 0.72 | 0.66 | 0.35 | 0.33 | 0.36 |
Secondary pore(1.7-10nm), % | 80.4 | 66.2 | 39.1 | 27.9 | 36.2 | ||
External surface area, m2/g | 191 | 182 | 299 | 255 | 170 | 159 | 180 |
Lattice constant, nm | 2.461 | 2.462 | 2.426 | 2.429 | 2.432 | 2.433 | 2.433 |
Relative crystallinity, % | 101 | 110 | 108 | 112 | 89 | 82 | 83 |
Average crystallite size, nm | 380 | 430 | 380 | 430 | 400 | 450 | 400 |
The physico-chemical property of 2 carrier of table and catalyst
Bearer number | TCAT-1 | TCAT-2 | TCCAT-1 | TCCAT-2 | TCCAT-3 |
Small-grain Y molecular sieve, wt% | 22 | 29 | 29 | 29 | 22 |
Amorphous silica-alumina, wt% | 58 | 51 | 51 | 51 | 58 |
Aluminium oxide, wt% | 20 | 20 | 20 | 20 | 20 |
Specific surface area, m2/g | 525 | 550 | 455 | 438 | 430 |
Pore volume, mL/g | 0.61 | 0.66 | 0.51 | 0.47 | 0.46 |
Pore size distribution(4-10nm), % | 76 | 68 | 49 | 46 | 43 |
Catalyst is numbered | CAT-1 | CAT-2 | CCAT-1 | CCAT-2 | CCAT-3 |
Specific surface area, m2/g | 405 | 420 | 325 | 309 | 301 |
Pore volume, mL/g | 0.57 | 0.60 | 0.46 | 0.43 | 0.42 |
Pore size distribution(4-10nm), % | 71 | 63 | 45 | 42 | 41 |
The invention described above catalyst CAT-1, CAT-2 and comparative example catalyst CCAT-1, CCAT-2 and CCAT-3 are carried out
Active evaluation test.Test is carried out on 200ml small hydrogenation devices, using one-stage serial technological process, raw materials used
Oil nature is shown in Table 3.Operating condition is as follows:Hydrogen dividing potential drop 14.7MPa, hydrogen to oil volume ratio 1500:1, air speed 1.5h- 1, control cracking zone
5~10 g/g of nitrogen content.Catalyst Activating Test the results are shown in Table 4.
3 raw material oil nature of table
Raw oil | Iranian VGO |
Density (20 DEG C), g/cm-3 | 0.9025 |
Boiling range, DEG C | 308~560 |
Condensation point, DEG C | 33 |
Acid number, mgKOH/g | 0.53 |
Carbon residue, wt% | 0.2 |
S, wt% | 1.5 |
N, wt% | 0.11 |
C, wt% | 84.93 |
H, wt% | 12.52 |
Aromatic hydrocarbons, wt% | 39.2 |
BMCI values | 41.5 |
Refractive power/nD 70 | 1.48570 |
4 catalyst activity evaluation result of table
Catalyst is numbered | CAT-1 | CAT-2 | CCAT-1 | CCAT-2 | CCAT-3 |
Reaction temperature, DEG C | 377 | 376 | 380 | 381 | 382 |
Product slates | |||||
<370 DEG C of conversion ratios, wt% | 64.8 | 65.0 | 64.8 | 64.9 | 64.9 |
Middle distillates oil selectivity, %(132~370 DEG C) | 86.5 | 87.4 | 81.8 | 81.9 | 82.0 |
Major product property | |||||
Jet fuel(132~282℃) | |||||
Freezing point, DEG C | <- 60 | <- 60 | <- 60 | <- 60 | <- 60 |
Aromatic hydrocarbons, wt% | 3.0 | 2.9 | 4.0 | 4.6 | 4.5 |
Smoke point, mm | 28 | 27 | 26 | 25 | 26 |
Diesel oil(282~370℃) | |||||
Cetane number | 63 | 64 | 59 | 58 | 57 |
Condensation point, DEG C | -5 | -7 | -2 | -1 | 0 |
Can be seen that by the evaluation result of 4 catalyst of table, the catalyst prepared by the present invention has on the basis of greater activity
There is good selectivity, product property is good.
Claims (25)
1. a kind of preparation method of hydrocracking catalyst, including:By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and with oxidation
Binding agent mechanical mixture, molding made by aluminum, are then dried and roasting, make catalyst carrier;In the catalyst carrier of gained
Load hydrogenation active metals component, drying and roasting, make catalyst;The preparation method of the small crystal grain Y-shaped molecular sieve, bag
Include:
(1) preparation of fine grain NaY type molecular sieve;
(2) by step(1)Fine grain NaY type molecular sieve be prepared into Na2Little crystal grain NH of O content≤1.5wt%4NaY;
(3) with little crystal grain NH4NaY is raw material, carries out first time hydrothermal treatment consists;
(4) molecular sieve for obtaining step (3) is with containing alkaline solution treatment;
(5) molecular sieve that step (4) is obtained is carried out into second hydrothermal treatment consists;
(6) the molecular sieve acid for obtaining step (5) and the mixed solution of ammonium salt are processed, and Jing is washed and is dried, and obtains small-grain Y
Type molecular sieve;
Small crystal grain NaY molecular sieve wherein used by step (1), its property are as follows:SiO2/Al2O3Mol ratio is not more than 6.0 and high
In 9.0, average grain diameter is 200~700nm, 800~1000 m of specific surface2/ g, 0.30/~0.45mL/g of pore volume, relatively
Degree of crystallinity is 90%~130%, and cell parameter is 2.460~2.470nm, relative Jing after roasting in 650 DEG C of air 3 hours to crystallize
Spend for more than 90%, Jing after 700 DEG C of water vapour hydrothermal treatment consists 2 hours, relative crystallinity is more than 90%.
2. in accordance with the method for claim 1, it is characterised in that:The SiO of small crystal grain NaY molecular sieve used2/Al2O3Mole
Than for 6.5~9.0.
3. in accordance with the method for claim 1, it is characterised in that:The SiO of small crystal grain NaY molecular sieve used2/Al2O3Mole
Than for 7.0~8.0.
4. in accordance with the method for claim 1, it is characterised in that:The average grain diameter of small crystal grain NaY molecular sieve used
For 300~500nm.
5. in accordance with the method for claim 1, it is characterised in that:Roast in 650 DEG C of air of small crystal grain NaY molecular sieve Jing used
After burning 3 hours, relative crystallinity is 90%~110%, and Jing after 700 DEG C of water vapour hydrothermal treatment consists 2 hours, relative crystallinity is 90%
~110%.
6. in accordance with the method for claim 1, it is characterised in that:The preparation method of small crystal grain NaY molecular sieve used, bag
Include:
I, preparation directed agents:Silicon source, silicon source, alkali source and water are fed intake according to following proportioning:(6~30) Na2O:Al2O3:(6~
30)SiO2:(100~460) H2O, after stirring, mixture at 0~20 DEG C is stirred to be aged to be obtained for 0.5~24 hour and is led
To agent;
II, using preparing amorphous silicon alumnium using carbonization predecessor, on the basis of the weight of the butt of amorphous silica-alumina predecessor,
The content that silicon is counted with silicon dioxide as 40wt%~75wt%;Its preparation process includes:
A, respectively preparation sodium aluminate solution and sodium silicate solution;
The part sodium silicate solution for adding step a to prepare in b, the sodium aluminate solution prepared to step a, then passes to CO2Gas,
Controlling reaction temperature is 10 ~ 40 DEG C, and the pH value for controlling cemented into bundles is 8 ~ 11;Wherein as the CO being passed through2Gas flow is accounted for and is always passed through
Amount 60% ~ 100% when, add remainder sodium silicate solution, wherein in step b, remainder sodium silicate solution is with silicon dioxide
Meter accounts for step b and adds 5wt% ~ 85wt% of the sodium silicate solution total amount in terms of silicon dioxide;
C, at the control temperature and pH value of step b, said mixture ventilation stablize 10 ~ 30 minutes;
III, prepare silica-alumina gel:By (0.5~6) Na2O:Al2O3:(8~15) SiO2:(100~460) H2O's always feeds intake mole
Than, 0~40 DEG C it is quick stir under conditions of water, silicon source, guiding are added in the amorphous silica-alumina predecessor obtained by step II
Agent and alkali source, and control ph is 9.5 ~ 12.0, uniform stirring obtains silica-alumina gel;Wherein directed agents addition accounts for sial and coagulates
The 1%~20% of glue weight,
Two step dynamic crystallizations of reactant mixture Jing obtained by IV, step III, then Jing filtrations, washing, are dried, obtain little crystal grain
NaY molecular sieve.
7. in accordance with the method for claim 6, it is characterised in that in step II, amorphous silica-alumina predecessor, with amorphous silicon
On the basis of the weight of the butt of aluminum predecessor, the content that silicon is counted with silicon dioxide is as 55 wt%~70wt%.
8. in accordance with the method for claim 6, it is characterised in that:Step b controlling reaction temperature is 15~35 DEG C.
9. in accordance with the method for claim 6, it is characterised in that:In step b, as the CO being passed through2Gas flow accounts for total intake
When 80% ~ 100%, remainder sodium silicate solution is added.
10. in accordance with the method for claim 6, it is characterised in that:In step b, remainder sodium silicate solution is with silicon dioxide
Meter accounts for step b and adds 30wt% ~ 70wt% of the sodium silicate solution total amount in terms of silicon dioxide.
11. in accordance with the method for claim 6, it is characterised in that in step I and III, and silicon source, alkali source are respectively selected from sodium silicate
And sodium hydroxide, in step I, silicon source is selected from sodium metaaluminate.
12. in accordance with the method for claim 6, it is characterised in that in step III, 10 ~ 30 DEG C of controlling reaction temperature, pH value 10
~11.
13. in accordance with the method for claim 6, it is characterised in that step IV adopts two step dynamic crystallizations, wherein the first stepping
The condition of Mobile state crystallization is as follows:At 50~90 DEG C, crystallization time is 0.5~18 hour to temperature control;Second step enters Mobile state
The condition of crystallization is as follows:At 80~140 DEG C, crystallization time is 3~10 hours to temperature control.
14. in accordance with the method for claim 6, it is characterised in that step IV adopts two step dynamic crystallizations, wherein the first stepping
The condition of Mobile state crystallization is as follows:At 60~80 DEG C, crystallization time is 1~10 hour to temperature control;It is brilliant that second step enters Mobile state
The condition of change is as follows:At 80~120 DEG C, crystallization time is 5~10 hours to temperature control.
15. in accordance with the method for claim 1, it is characterised in that step(2)In, with fine grain NaY type molecular sieve as raw material,
With containing H+The aqueous solution of ammonium salt exchange 0.5~3.0 hour at 70~120 DEG C;Containing H+Ammonium salt aqueous solution in, H+It is dense
Spend for 0.005~0.5mol/L, NH4 +Concentration be 0.5~5.0mol/L, molecular sieve exchange serosity in concentration be 0.05~
0.50 g/mL, repeated exchanged l~5 time.
16. in accordance with the method for claim 15, it is characterised in that step(2)In, described ammonium salt is ammonium chloride, carbonic acid
One or more in ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, provides H in aqueous solution+Acid be salt
Acid, carbonic acid, nitric acid, one or more in sulphuric acid.
17. in accordance with the method for claim 1, it is characterised in that step(3)Described first time hydrothermal treatment consists temperature is 500
DEG C~700 DEG C, water vapor pressure is 0.01~1.0MPa, and process time is 1.0~10.0 hours.
18. in accordance with the method for claim 1, it is characterised in that step(4)By step(3)The molecular sieve for obtaining and the water of alkali
Solution is beaten mix homogeneously, and maintains 1~4h of stir process under 60~120 DEG C of temperature conditionss, filters, washes;Described alkali
Selected from NaOH, KOH or NaOH and the mixture of KOH, the concentration of the aqueous solution of alkali is 0.1~3.0 mol/L, molecular sieve in serosity
Concentration be 0.05~1.0g/mL.
19. in accordance with the method for claim 1, it is characterised in that step(5)Second described hydrothermal treatment consists temperature is 500
~800 DEG C, water vapor pressure is 0.01~1.0MPa, and process time is 1.0~10.0 hours, and second hydrothermal treatment consists temperature is high
In or be equal to first time hydrothermal treatment consists temperature it is identical.
20. in accordance with the method for claim 1, it is characterised in that step(6)In, processed with the mixed solution of acid and ammonium salt,
Acid therein be hydrochloric acid, carbonic acid, nitric acid, one or more in sulphuric acid, containing NH4 +Salt be in the ammonium salt containing above acid group one
Plant or various;H in mixed solution+Concentration be 0.05~0.6mol/L, NH4 +Concentration be 0.5~3.0mol/L, exchange temperature
For 70~120 DEG C, the concentration for exchanging molecular sieve in serosity is 0.1~0.5g/mL, and swap time is 0.5~3.0 hour, is exchanged
Step may be repeated 1~4 time.
21. in accordance with the method for claim 1, it is characterised in that:Used by mixing with small crystal grain Y-shaped molecular sieve and binding agent
SiO in amorphous silica-alumina2Weight content be 20%~60%, the pore volume of amorphous silica-alumina is 0.6~1.1 mL/g, specific surface
Product is 300~500 m2/g。
22. in accordance with the method for claim 1, it is characterised in that:The condition of carrier drying and roasting is as follows:80 DEG C~
It is dried 3~10 hours and in 500 DEG C~600 DEG C roastings 3~6 hours at a temperature of 150 DEG C;The drying of catalyst and roasting condition
It is as follows:L~12 hour are dried at 100 DEG C~150 DEG C, then in 450 DEG C~550 DEG C roastings 3~6 hours.
23. in accordance with the method for claim 1, it is characterised in that:Described carrier of hydrocracking catalyst, with the weight of carrier
On the basis of amount, its composition includes:The content of small crystal grain Y-shaped molecular sieve is 5wt%~40wt%, and the content of amorphous silica-alumina is
20wt%~65wt%, the content of aluminium oxide is 10wt%~40wt%.
24. in accordance with the method for claim 1, it is characterised in that:Described hydrogenation active metals are vib and/or the
The metal of VIII race, vib metals are molybdenum and/or tungsten, and the metal of the VIIIth race is cobalt and/or nickel.
25. in accordance with the method for claim 24, it is characterised in that:On the basis of the weight of catalyst, vib metals with
The content that the content of oxide meter is 10wt%~30wt% and group VIII metal to be counted with oxide as 4wt%~10wt%, carrier
Content is 61wt%~86wt%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410045554.3A CN104826653B (en) | 2014-02-08 | 2014-02-08 | A kind of method for preparing hydrocracking catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410045554.3A CN104826653B (en) | 2014-02-08 | 2014-02-08 | A kind of method for preparing hydrocracking catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104826653A CN104826653A (en) | 2015-08-12 |
CN104826653B true CN104826653B (en) | 2017-03-29 |
Family
ID=53805063
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410045554.3A Active CN104826653B (en) | 2014-02-08 | 2014-02-08 | A kind of method for preparing hydrocracking catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104826653B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107303494B (en) * | 2016-04-22 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
CN107303493B (en) * | 2016-04-22 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of preparation method of Catalyst For Single-stage Hydrocracking |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1178193A (en) * | 1996-09-27 | 1998-04-08 | 中国石油化工总公司 | Modified zeolite and manufacture thereof |
CN101618348A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
CN102049280A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing small crystal grain Y-shaped molecular sieve and preparation method thereof |
CN103100441A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Carrier material containing molecular sieve and amorphous silica-alumina and preparation method thereof |
CN103100403A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
-
2014
- 2014-02-08 CN CN201410045554.3A patent/CN104826653B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1178193A (en) * | 1996-09-27 | 1998-04-08 | 中国石油化工总公司 | Modified zeolite and manufacture thereof |
CN101618348A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
CN102049280A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing small crystal grain Y-shaped molecular sieve and preparation method thereof |
CN103100441A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Carrier material containing molecular sieve and amorphous silica-alumina and preparation method thereof |
CN103100403A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN104826653A (en) | 2015-08-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104588073B (en) | Hydrogenation dearomatization catalyst and preparation method thereof | |
CN104588076B (en) | Hydrocracking catalyst and preparation method thereof | |
CN104826645B (en) | A kind of preparation method of hydrocracking catalyst | |
CN104826652B (en) | The method for preparing hydrocracking catalyst | |
CN104588078B (en) | Hydrocracking catalyst and preparation method thereof | |
CN104826667B (en) | The method for preparing carrier of hydrocracking catalyst | |
CN104588122B (en) | Hydrocracking catalyst carrier and preparation method thereof | |
CN104826653B (en) | A kind of method for preparing hydrocracking catalyst | |
CN106140281B (en) | A kind of preparation method of middle oil type hydrocracking catalyst | |
CN105713657B (en) | Hydrocracking method | |
CN104826651B (en) | The preparation method of hydrocracking catalyst | |
CN106140282B (en) | Middle oil type hydrocracking catalyst and preparation method thereof | |
CN104588077B (en) | The preparation method of hydrocracking catalyst | |
CN104826650B (en) | A kind of method preparing catalytic hydro-dearomatization catalyst | |
CN104826646B (en) | Preparation method for hydrocracking catalyst carrier | |
CN104826665B (en) | A kind of method for preparing carrier of hydrocracking catalyst | |
CN104588124B (en) | Preparation method of hydrocracking catalyst carrier | |
CN106140319A (en) | A kind of preparation method of middle oil type hydrocracking catalyst carrier | |
CN104588123B (en) | Preparation method of hydrocracking catalyst carrier | |
CN106140250B (en) | A kind of preparation method of hydrocracking catalyst | |
CN104588121B (en) | Hydrocracking catalyst carrier and preparation method thereof | |
CN104588080B (en) | A kind of preparation method of hydrocracking catalyst | |
CN104826666B (en) | The preparation method of carrier of hydrocracking catalyst | |
CN104826648B (en) | A kind of preparation method of catalytic hydro-dearomatization catalyst | |
CN106140318B (en) | Middle oil type hydrocracking catalyst carrier and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
EXSB | Decision made by sipo to initiate substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |