CN106669783B - The preparation method of hydrocracking catalyst - Google Patents
The preparation method of hydrocracking catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of hydrocracking catalyst.This method comprises: forming mixed serum containing the alkaline solution of magnesium and aluminium, the acid solution of silicon and tungstenic；The alkaline solution of nickeliferous acid solution and tungstenic forms mixed serum；Then above two slurries mixing, and pH value is adjusted, after aging, Y molecular sieve and macromolecular polyethylene glycol are added in slurries after mixed grinding, filtered, are dried；Hydrocracking catalyst is made in reshaping.The raising of the hydrogenation activity of the catalyst and effective cooperation of acid function improve the resistance to nitrogen ability of catalyst, make catalyst under the conditions of reactant nitrogen content is higher still with good hydrocracking activity and the performance for preferably delaying carbon deposit to generate.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst, especially a kind of nitrogen-resistant type fecund intermediate oil
The preparation method of hydrocracking catalyst.
Background technique
In recent years, the fast-developing of world economy drives transportation to be continuously increased the demand of intermediate oil,
Crude oil production amount is also growing therewith, leads to heaviness, the in poor quality trend further expansion of crude oil.Simultaneously fuel
The pollutant of burning and exhausting is also increasingly taken seriously to environment bring for the survival of mankind harm, stringenter environmental protection
Regulation is also put into effect therewith.Oil plant is faced with fraction between the increase of Raw material processing difficulty, product quality upgrading, city's field alignment as a result,
Oily demand continues many challenges such as vigorous.
Being hydrocracked can be heavy oil conversion at the fuel oil being of high quality, and product can sell without purification and make
With, therefore hydrocracking technology becomes best one of the manufacturing process of processing poor quality, heavy charge production high-grade fuel oil.
Macromolecular basic nitrogen compound in feedstock oil, which is easily adsorbed on the acid centre of catalyst, makes catalyst poisoning, coking
Reduce the operation cycle of catalyst.To the raw material of higher nitrogen content, when carrying out one-stage serial or two sections of process hydrotreatings, in original
Before material is contacted with containing molecular sieve catalyst, generally nitrogen content will be made to be reduced to make to be hydrocracked by unifining process
Catalyst activity preferably plays in permitted range.
General industry application contain molecular sieve hydrocracking catalyst, it is desirable that Control of Nitrogen Content between 1~20 μ g/g,
When cracking zone feeds nitrogen content to 50 μ g/g or so, Cracking catalyst just needs higher reaction temperature, and high reaction temperature
Degree is unfavorable for its active effective performance, while meeting accelerator activator coking, inactivation, reduces the service life of catalyst, refines oil
Factory generally by cracking zone charging Control of Nitrogen Content in 20 μ g/g hereinafter, but when the nitrogen content in VGO is in 200~2000 μ g/g,
Effluent nitrogen content is dropped to by prerefining relatively difficult within the scope of this, harsher treatment conditions must be selected to split to realize
Change requirement of the catalyst to charging nitrogen content.Though such as improving, temperature, reducing air speed means, to can compensate for catalyst for refining active
Deficiency, but will lead to catalyst for refining rapid deactivation, shorten its service life.
The higher Hydrogenation of hydrocracking catalyst active metal can comply with nitride hydrodenitrogeneration and first hydrogen be added to make aromatic ring
It is saturated again the reaction mechanism of C-N key fracture denitrogenation, accelerates nitride mostly fast conversion, plays and acidity of catalyst center is protected
Effect, improve the resistance to nitrogen ability of catalyst, make catalyst under the conditions of reactant nitrogen content is higher still have it is good plus
Hydrogen lytic activity and the performance for preferably delaying carbon deposit to generate.
The key reaction of middle oil type hydrocracking catalyst is that dehydrogenation of saturated hydrocarbon is made to generate active alkene intermediates, by means of urging
Agent acid centre generates cracking after carbonium ion, while polycyclic aromatic hydrocarbon, cycloalkane and unsaturated crackate being made to add hydrogen full
With.It is required that catalyst will have moderate acid and force hydrogen activity.
Hydrocracking catalyst acidic components molecular sieve have high crystallinity, low cell parameter, high surface area and
More secondary pore, infrared acidity is lower, and acid site number is more, when not having the characteristics such as strong acid center substantially, can avoid in raw material
Macromolecular basic nitrogen compound strong acid center it is strong absorption caused by catalyst poisoning inactivation and raw material in strong acid center
Catalyst coking and deactivation caused by multidigit condensation reaction can be improved the anti-nitrogen ability of molecular sieve catalyst, extend molecular sieve catalytic
The service life of agent；Processable inferior raw material is conducive to improve the diffusion velocity of raw material and product, reduces the second pyrolysis of product,
Improve the middle distillates oil selectivity of catalyst.
Amorphous silicon Al catalysts have high middle distillates oil selectivity, but activity is low, and operating flexibility is poor, by amorphous silica-alumina
It combines to cooperate with nitrogen-resistant type molecular sieve and plays respective advantage, improve nitrogen resistance, activity and the middle oil selection of catalyst
Property.
The common preparation method of hydrocracking catalyst is kneading method, coprecipitation method, infusion process at present.These types of preparation method
Respectively there are an advantage and disadvantage, the kneading together such as kneading method active metal and acidic components, carrier, auxiliary agent, being limited by preparation method cannot make
Each active component reaches well-proportioned dispersion, and catalyst localized metallic or acidic components can be made, which to assemble, influences its active effective hair
It waves or catalyst local reaction leads to catalyst coking and deactivation strongly.The method that the preparation of infusion process carrier generally uses kneading, silicon
Aluminium and molecular sieve are also unable to reach well-proportioned dispersion in kneading process, and metal is introduced by infusion process, in drying, roasted
Intergranular capillary force can make active component reunite in journey, form larger-size particle, reduce point of active metal
Divergence.Coprecipitation method can make metal and carrier, acidic components reach well-proportioned dispersion, be formed between active metal and carrier weaker
Effect, but the distribution of active metal on a catalyst from inside to outside is substantially uniform, when reactant and catalyst contact,
The part metals that reactant cannot reach are changing to invalid component, to reduce the utilization rate of active metal；Co-precipitation preparation
Hydrocracking catalyst molecular sieve is usually to be distributed in sediment slurry, if protection is not added, cell channels can be also deposited
Grain blocking, prevents the partial function of molecular sieve from being not fully exerted.
CN101172260A discloses a kind of preparation method of hydrogenation catalyst, and carrier material uses amorphous silica-alumina,
Molecular sieve is introduced during plastic；In the preparation method for the hydrocracking catalyst that CN101239324A is disclosed, Y molecular sieve is
It is directly added into coprecipitation mixture and is introduced into catalyst, the above method can make cell channels be blocked, and influence its acid function
The efficient performance of energy.
CN1253988A discloses a kind of hydrocracking catalyst of nitrogen-resistant type fecund intermediate oil, and CN1253989A is public
A kind of heavy hydrocarbons hydrocraking catalyst and preparation method thereof is opened, the preparation method of both catalyst all uses active gold
Belong to the method for carrier coprecipitation, although active metal can reach with carrier and acidic components it is evenly dispersed, active metal and
The co-precipitation of carrier auxiliary agent can cause mutually to wrap up, and expose some metal components cannot sufficiently in body phase, become invalid
Component, each active component of prepared catalyst can not efficiently play a role.
Summary of the invention
Aiming at the shortcomings in the prior art, the present invention provides a kind of preparation methods of hydrocracking catalyst.This method
The catalyst of preparation can improve the Hydrogenation of active metal by a relatively large margin, and cooperate with acidic components, improve the resistance to of catalyst
Nitrogen ability makes catalyst still have good hydrocracking activity under the conditions of reactant nitrogen content is higher and preferably delay
The performance that carbon deposit generates.
The preparation method of hydrocracking catalyst of the present invention, comprising:
(1) the alkaline solution B of tungstenic is added into the acid solution A containing magnesium and aluminium, silicon, until pH is 10~12, is mixed
Close slurries；
(2) the alkaline solution D of tungstenic is added into nickeliferous acid solution C, until pH is 4~6, obtains mixed serum；
(3) step (1) resulting slurries are mixed with step (2) resulting slurries, and adjusts pH value to 7~9, through aging
Afterwards, Y molecular sieve and macromolecular polyethylene glycol are added in slurries after mixed grinding, are uniformly mixed, are filtered, dried；
(4) by step (3) resulting material forming, washing, drying and roasting obtain hydrocracking catalyst.
In step (1) in the alkaline solution B of tungstenic and step (2) in the alkaline solution D of tungstenic the additional amount of tungsten mole
Than for 1:1 ~ 1:15, preferably 1:1 ~ 1:8.
Step (1) containing magnesium and aluminium, silicon acid solution A in, silicon and the molar ratio of aluminium based on the element are 0.2 ~ 5.0, preferably
0.5~3.0。
Required catalyst promoter can be added in step (1) and/or step (2).Auxiliary agent generally comprises P, F, B, Zr, Ti
One or more of Deng.The method that auxiliary agent is added uses conventional method in that art.The additional amount of auxiliary agent accounts for hydrocracking catalyst
The 25% of agent weight is hereinafter, preferably 1%~15%.
The Y molecular sieve that step (2) is introduced into can preferably be adopted using conventional use of Y molecular sieve in hydrocracking catalyst
With modified Y molecular sieve, Y molecular sieve method of modifying is carried out by method described in ZL96119840.0, and property is as follows: SiO2/
Al2O3Weight ratio be 9~20, cell parameter be 2.380~2.423nm, relative crystallinity > 100%, specific surface area be 750~
950 m2/ g, infrared acidity are 0.1~0.3mmol/g.
In step (2), Y molecular sieve is as follows through mixed grinding process with macromolecular polyethylene glycol: by macromolecular polyethylene glycol
It is dissolved in water, Y molecular sieve is added, slurries are made, then grind 10~120min repeatedly in mortar or colloid mill.Wherein, greatly
The weight ratio of molecule polyethylene glycol and Y molecular sieve is 1:10 ~ 1:100, preferably 1:20 ~ 1:100；The molecular weight of polyethylene glycol is
1000 ~ 10000, preferably 2000 ~ 8000.
Conventional forming method, such as extrusion forming etc. can be used in step (4).The shape of catalyst can according to need system
Slabbing, spherical, cylindrical bars and irregular bar (such as clover, bunge bedstraw herb), preferably cylindrical bars and irregular strip.In forming process
In, suitable shaping assistant, such as extrusion aid etc. can be added.Wherein water purification can be used in washing and/or ethanol solution is washed
It washs.
In step (4), dry and roasting condition is as follows: it is 2.0 ~ 6.0 hours dry at 50 ~ 120 DEG C, it is roasted at 450 ~ 600 DEG C
It burns 3.0 ~ 6.0 hours.
In the hydrocracking catalyst of the method for the present invention preparation, on the basis of the weight of hydrocracking catalyst, tungsten oxide
Content with nickel oxide is 15% ~ 50%, preferably 20% ~ 40%, and the content of magnesia is 3%~10%, the content of amorphous silica-alumina
It is 20% ~ 80%, preferably 30% ~ 75%, the content of Y molecular sieve is 5% ~ 35%, preferably 10% ~ 30%.
In the hydrocracking catalyst of the method for the present invention preparation, the molar ratio of W and Ni is 1:10 ~ 10:1, preferably 1:5 ~
5:1.
The property of hydrocracking catalyst of the present invention is as follows: 0.26 ~ 0.50mL/g of Kong Rong, 180 ~ 410m of specific surface2/g。
In the intermediate processing that hydrocracking catalyst preparation method of the present invention uses, active metal is mainly with nickel tungstate and tungsten
Sour magnesium form precipitating, can preferably cooperate, and easy vulcanization forms high activity phase, thus improve catalyst plus hydrogen work
Property, meanwhile, when adding Y molecular sieve, first with macromolecular polyethylene glycol mixed grinding, molecular sieve surface can be made to form one layer of macromolecule
Film avoids its cell channels and is blocked, is effectively protected the unimpeded of molecular sieve pore passage, the performance of Y molecular sieve can be made to obtain
It gives full play to, effective cooperation of the raising of the hydrogenation activity of the catalyst and acid function, has complied with hydrocracking process as a result,
To improve middle distillates oil selectivity and anti-nitrogen performance reaction active site demand, for heavy hydrocarbon single-stage hydrocraking process have compared with
Good anti-nitride poisoning capability can tolerate the higher nitrogen content of raw material for tandem process process.
Specific embodiment
Hydrocracking catalyst preparation method provided by the invention, specifically includes:
(1) the alkaline solution B of tungstenic is added into the acid solution A containing magnesium and aluminium, silicon, until pH is 10~12, is mixed
Close slurries；
According to catalytic component content match prepare the acid solution A containing magnesium and aluminium, silicon, aluminium containing salt can be aluminium chloride,
One or more of aluminum nitrate, aluminum sulfate etc. can be magnesium chloride, magnesium nitrate containing magnesium salts, in the soluble magnesium salts such as magnesium sulfate
One or more, silicon source can be one or more of waterglass, silica solution etc.；Acidity can use hydrochloric acid, nitric acid, acetic acid
It adjusts etc. one or more of inorganic or organic acid, is advisable so that acidic salt solution is not muddy；
Auxiliary agent can need introduce in acid solution A according to the ratio according to catalyst, and auxiliary agent preferred P and/or Si, phosphorus source can be with
It is one or more of phosphoric acid, phosphorous acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate etc.；
The alkaline solution B of tungstenic is prepared, tungsten salt can be one or more of sodium tungstate, ammonium metatungstate etc., preferably
Sodium tungstate, the alkaline solution B of tungstenic, which can according to need, is added alkali water-soluble compound, such as sodium hydroxide, sodium carbonate, carbonic acid
One of hydrogen sodium, ammonium hydroxide, urea etc. are a variety of, preferably sodium hydroxide, and the concentration of sodium hydroxide can be any feasible
Ratio, preferably in 1wt% ~ 20wt%；
Acid solution A and alkaline solution B are subjected to acid-base neutralization plastic, gelling temperature is 30 ~ 80 DEG C, and when cemented into bundles starches
The pH of liquid is 10~12, and gelation time is 0.2 ~ 2.0h, and the method that the method for plastic can use cocurrent can also be used alkali
Property solution method that acid solution plastic is added, the preferred method of cocurrent；
(2) the alkaline solution D of tungstenic is added into nickeliferous acid solution C, until pH is 4~6, obtains mixed serum；
Prepare nickeliferous acid solution C according to catalytic component content proportion, containing nickel salt can be nickel sulfate, nickel nitrate,
One or more of nickel chloride, nickel oxalate etc.；Acidity can use hydrochloric acid, nitric acid, and acetic acid etc. is inorganic or one of organic acid
Or several adjustings, it is advisable so that acidic salt solution is not muddy；
The alkaline solution D of tungstenic is prepared, tungsten salt can be one or more of sodium tungstate, ammonium metatungstate etc., preferably
Sodium tungstate, the alkaline solution D of tungstenic, which can according to need, is added alkali water-soluble compound, such as sodium hydroxide, sodium carbonate, carbonic acid
One of hydrogen sodium, ammonium hydroxide, urea etc. are a variety of, preferably sodium hydroxide, and the concentration of sodium hydroxide can be any feasible
Ratio, preferably in 1wt% ~ 20wt%；
Acid solution C and alkaline solution D are subjected to acid-base neutralization plastic, gelling temperature is 30 ~ 80 DEG C, and when cemented into bundles starches
The pH of liquid is 4~6, and gelation time is 0.2 ~ 2.0h, and the method that the method for plastic can use cocurrent, can also use will be alkaline
The method that acid solution plastic is added in solution, the preferably method of cocurrent；
(3) mixing, aging plus molecular sieve
Step (1) resulting slurries are mixed with step (2) resulting slurries, adjust the pH value of mixed serum to 7~9,
Stir 10~30min, adjustment temperature to 70~95 DEG C aging 1~4 hour, by Y molecular sieve with macromolecular polyethylene glycol through mixing
It is added in slurries, mixes after grinding, filtering, drying；The drying condition is as follows: 40 ~ 100 DEG C of drying temperature, drying time 4
~10h；
(4) it forms, catalyst is made
Shaping assistant is added in the material that step (3) obtains to form, is washed, dry, roasting obtains catalysis of the present invention
Agent.Wherein water purification can be used in washing and/or ethanol solution is washed.Wash temperature is generally 50 DEG C~70 DEG C, embathes liquid measure
It is advisable with 10~20 times of catalyst preparation amount, is dissolved in cleaning solution so that polyethylene glycol is as much as possible, is removing impurity
While remove polyethylene glycol.The shape of catalyst, which can according to need, is made sheet, spherical, cylindrical bars and irregular strip (such as three
Leaf grass, bunge bedstraw herb), preferably cylindrical bars and irregular strip；Dry and roasting condition is as follows: small in 50 ~ 120 DEG C of dryings 2.0 ~ 6.0
When, it is roasted 3.0 ~ 6.0 hours at 450 ~ 600 DEG C.
The scheme and effect that present invention will be further explained by specific examples below.In the present invention, wt% is quality point
Number, v% is volume fraction.The Kong Rong and specific surface of catalyst of the present invention and comparative example catalyst and added molecular sieve are used
Low temperature liquid nitrogen determination of adsorption method；Mechanical strength is measured using side pressure method；The distribution of molecular sieve acid strength uses Temperature Programmed Desorption
(TPD), molecular sieve silica alumina ratio uses chemical method；Molecular sieve crystallinity, cell parameter use x-ray diffraction method；Molecular sieve meleic acid
Degree is measured using infra-red sepectrometry.
Embodiment 1
3000mL water purification is added in a plastic cans, is warming up to 50 DEG C；
2000mL water purification is added in a vessel, 15mL concentrated hydrochloric acid, 460g aluminium chloride, 25g magnesium chloride, stirring keeps its molten
Solution instills and contains SiO2Dilute water glass solution 500mL of 131g/L, stirs evenly, is configured to acid solution A；
Compound concentration is the sodium hydroxide solution 1000mL of 15wt% in a vessel, and 25g sodium tungstate is added, and is stirred molten
Solution, is configured to alkaline solution B；
The flow velocity of fixed acidity solution A, adjusts the flow velocity of alkaline solution B, and cocurrent is added in plastic cans, controls gelling temperature
It is 50 DEG C, slurries pH is that plastic is completed in 10.8 ± 0.2,30min, and at the end of reaction, solution A and B solution must be all added
In plastic cans, 10min is stirred after cemented into bundles；
(2) 3000L water purification is added in a plastic cans, is warming up to 45 DEG C；
2000mL water purification is added in a vessel, 88g nickel chloride, 15mL concentrated hydrochloric acid is added, stirring and dissolving is configured to acid
Property solution C；
Compound concentration is the sodium hydroxide solution 600mL of 5wt% in a vessel, and 120g sodium tungstate is added, and is stirred molten
Solution, is configured to alkaline solution D；
The flow velocity of fixed acidity solution C, adjusts the flow velocity of alkaline solution D, and cocurrent is added in plastic cans, controls gelling temperature
It is 45 DEG C, slurries pH is that plastic is completed in 5.8 ± 0.2,30min, and at the end of reaction, C solution and solution D must be all added into
In glue tank, 10min is stirred after plastic；
(3) slurries obtained by step (1) are added in step (2) resulting slurries, stir 20min, after mixing, adjustment
The pH value of slurries be 8.0 ± 0.2, be warming up to 80 DEG C of agings 3 hours, after aging, by mixed serum be divided into 5 parts it is standby
With being denoted as mixed serum A；
(4) 200mL water purification is added in a vessel, the polyethylene glycol stirring and dissolving of 5.4g molecular weight 6000 is added, adds
Enter 181g Y molecular sieve and slurries are made, grind 30min or so repeatedly in colloid mill, be divided into 10 parts, is denoted as molecule screening the pulp
Liquid B1；20mL water purification is added in a vessel, the polyethylene glycol stirring and dissolving of 0.2g molecular weight 6000 is added, 18g Y is added
System with molecular sieve for preparing grinds 40min or so at slurries repeatedly in mortar, is denoted as molecular sieve pulp B2；It is added in a vessel
The polyethylene glycol stirring and dissolving of 1g molecular weight 4000 is added in 20mL water purification, 18g Y molecular sieve is added, slurries are made, in mortar
40min or so is ground repeatedly, is denoted as molecular sieve pulp B3；Y molecular sieve property is SiO2/Al2O3Weight ratio 9.5, specific surface area
For 785m2/ g, Kong Rongwei 0.391mL/g, relative crystallinity 102, infrared acidity 0.210mmol/g；
(5) it takes 1 part of step (3) to obtain mixed serum A, 1 part of molecular sieve pulp B1 is added, stir 10min, filtering, filter cake
It is 1 hour dry at 80 DEG C, extrusion aid is added and rolls, with the cylinder orifice plate extruded moulding of diameter 2.8mm, at profile bar 5wt% ethyl alcohol
Solution 1500mL embathes 4 times in 55 DEG C of waters bath with thermostatic control, is embathed 2 times with 1500mL water purification room temperature, and it is left to wash 10min every time
The right side obtains shaping of catalyst item, 5 hours dry at 120 DEG C, roasts 4 hours at 500 DEG C, obtains catalyst A of the present invention.
Embodiment 2
Catalyst whole preparation process is with embodiment 1, the difference is that catalyst preparation inventory is the 1/ of embodiment
Sodium tungstate 7g is added when 5, alkaline solution B are prepared, sodium tungstate 22g is added when alkaline solution D is prepared, is added and implements in mixed serum
Molecular sieve pulp B1 is a in step (4) in example 1, obtains catalyst B of the present invention.
Embodiment 3
Catalyst whole preparation process is with embodiment 1, the difference is that catalyst preparation inventory is the 1/ of embodiment
Sodium tungstate 3.8g is added when 5, alkaline solution B are prepared, sodium tungstate 25.4g is added when alkaline solution D is prepared, is added in mixed serum
Molecular sieve pulp B1 is a in step (4) in embodiment 1, obtains catalyst C of the present invention.
Embodiment 4
Mixed serum A is a in 1 step of Example (3), and molecular sieve pulp B2 portion is mixed in step (4) in embodiment 1
It closes, other processes obtain catalyst D of the present invention with embodiment 1.
Embodiment 5
Mixed serum A is a in 1 step of Example (3), and molecular sieve pulp B3 portion is mixed in step (4) in embodiment 1
It closes, other processes obtain catalyst E of the present invention with embodiment 1.
Embodiment 6
Catalyst whole preparation process is with embodiment 1, the difference is that catalyst preparation inventory is the 1/ of embodiment
Magnesium chloride 2.5g, aluminium chloride 95g are added when 5, acid solution A are prepared, is added in mixed serum in embodiment 1 in step (4) point
Sub- screening the pulp liquid B1 is a, and the other the same as in Example 1 obtains catalyst F of the present invention.
Embodiment 7
Catalyst whole preparation process is with embodiment 1, the difference is that catalyst preparation inventory is the 1/ of embodiment
Magnesium chloride 10g, aluminium chloride 87g are added when 5, acid solution A are prepared, molecule in step (4) is added in embodiment 1 in mixed serum
Screening the pulp liquid B1 is a, and the other the same as in Example 1 obtains catalyst G of the present invention.
Embodiment 8
Catalyst whole preparation process is with embodiment 1, the difference is that catalyst preparation inventory is the 1/ of embodiment
Magnesium chloride 18g, aluminium chloride 75g are added when 5, acid solution A are prepared, molecule in step (4) is added in embodiment 1 in mixed serum
Screening the pulp liquid B1 is a, and the other the same as in Example 1 obtains catalyst H of the present invention.
Comparative example 1
500mL water purification, 17.5g nickel chloride are added into dissolving tank 1, stirring and dissolving is configured to acid working solution A.To
Addition 500mL water purification, 27.5g sodium tungstate, 132g sodium metaaluminate, stirring and dissolving are configured to alkaline working solution B in dissolving tank 2.
400mL water purification is added into reactor tank, is warming up to 60 DEG C.In the case of stirring, reaction is added in solution A and solution B cocurrent
Plastic in tank, gelling temperature are 60 DEG C, and gelation time is 0.5 hour, and the pH of slurries is 8.0 during plastic, after cemented into bundles
Aging 1 hour, molecular sieve pulp B1 portion in 1 step of embodiment (3) is added, stirring 10min filtering, filter cake is at 80 DEG C dry 1
Hour, extrusion aid is added and rolls, with the cylinder orifice plate extruded moulding of diameter 2.8mm；At profile bar washing process with embodiment 1, wash
The shaped catalyst item of net impurity is 5 hours dry at 120 DEG C, roasts 4 hours at 500 DEG C, obtains comparative example catalyst I.
Comparative example 2
Catalyst preparation process is with comparative example 1, when difference is that acid solution A is prepared, adds 5g magnesium chloride, precipitating mixing
Molecular sieve pulp B1 portion, other same comparative examples 1 in 1 step of embodiment (3) are added in slurries and obtain this comparative example catalyst J.
Comparative example 3
Catalyst whole preparation process is with embodiment 1, the difference is that catalyst preparation inventory is the 1/ of embodiment
Magnesium chloride is not added in 5, acid solution A when preparing, precipitate and molecular sieve pulp B1 mono- in 1 step of embodiment (3) is added in mixed serum
Part, other same comparative examples 1 obtain this comparative example catalyst K.
Catalyst of the present invention and comparative example catalyst composition and physico-chemical property such as Tables 1 and 2.
The composition of table 1 catalyst of the present invention and comparative example catalyst
The property of table 2 catalyst of the present invention and comparative example catalyst
Embodiment
9
The anti-nitrogen and plus hydrogen open-loop performance evaluation of catalyst of the present invention and comparative example catalyst.
The evaluation procedure of catalyst of the present invention and comparative example catalyst is as follows:
Catalyst of the present invention is first vulcanized on micro-reactor with comparative example catalyst；1000ppm containing pyridine is used again
Normal heptane be raw material, temperature be 390 DEG C, hydrogen pressure be 6.0MPa, H2/ normal heptane volume ratio is 1500/1, air speed 1.5h-1
Under conditions of carry out 8hr toxic reaction；Then using toluene as raw material, temperature is 380 DEG C, and hydrogen pressure is 6.0MPa, H2/ toluene body
Product is than being 1500/1, air speed 1.5h-1Under conditions of reacted, after stable reaction, pass through the conversion ratio of toluene, methyl ring
The accounting of hexane and isomery C7 come evaluate catalyst anti-nitrogen and add hydrogen open-loop performance.Toluene reaction product Varian3800 type
The analysis of capillary on-line gas chromatography.
The high anti-nitrogen performance of catalyst and high middle oil yield need catalyst in the higher situation of raw material nitrogen content, still
With high conversion ratio and high plus hydrogen open-loop performance and non-excessive fragmentation.What toluene reacted on the catalyst after nitrogen poisoning
Conversion ratio is higher, and its anti-nitrogen performance of explanation is stronger, and the accounting of hexahydrotoluene and isomery C7 are higher in reaction product illustrates that it adds hydrogen
Open-loop performance is stronger.
After catalyst of the present invention and the poisoning of comparative example catalyst nitrogen plus hydrogen destructive characteristics evaluation data are listed in table 3.
Conversion ratio and plus hydrogen open-loop products of 3 toluene of table on nitrogen poisoned catalyst
Table 3 statistics indicate that catalyst of the present invention plus hydrogen open loop ability and anti-nitride poisoning capability be catalyzed compared with comparative example
Agent has a more substantial increase.
Claims (13)
1. a kind of preparation method of hydrocracking catalyst, comprising:
(1) the alkaline solution B of tungstenic is added into the acid solution A containing magnesium and aluminium, silicon, until pH is 10~12, obtains mixing slurry
Liquid；
(2) the alkaline solution D of tungstenic is added into nickeliferous acid solution C, until pH is 4~6, obtains mixed serum；
(3) step (1) resulting slurries are mixed with step (2) resulting slurries, and adjusts pH value to 7~9, after aging,
Y molecular sieve and macromolecular polyethylene glycol are added in slurries after mixed grinding, is uniformly mixed, is filtered, dried；
(4) by step (3) resulting material forming, washing, drying and roasting obtain hydrocracking catalyst.
2. according to the method for claim 1, it is characterised in that: in step (1) in the alkaline solution B of tungstenic and step (2)
The molar ratio of the additional amount of tungsten is 1:1 ~ 1:15 in the alkaline solution D of tungstenic.
3. according to the method for claim 1, it is characterised in that: step (1) containing magnesium and aluminium, silicon acid solution A in, silicon with
The molar ratio of aluminium based on the element is 0.2 ~ 5.0.
4. according to the method for claim 1, it is characterised in that: in step (1), by acid solution A be added alkaline solution B into
The condition of row plastic is as follows: gelling temperature is 30 ~ 80 DEG C, and the pH of slurries is 10~12 when cemented into bundles, gelation time is 0.2 ~
2.0h。
5. according to the method for claim 1, it is characterised in that: in step (2), by acid solution C be added alkaline solution D into
The condition of row plastic is as follows: gelling temperature is 30 ~ 80 DEG C, and the pH of slurries is 4~6 when cemented into bundles, gelation time is 0.2 ~
2.0h。
6. according to the method for claim 1, it is characterised in that: in step (3), the aging condition is as follows: 70~95 DEG C
Aging 1~4 hour, the drying condition was as follows: 40 ~ 100 DEG C of drying temperature, 4 ~ 10h of drying time.
7. according to the method for claim 1, it is characterised in that: the catalysis needed for being added in step (1) and/or step (2)
Agent aid, auxiliary agent include one or more of P, F, B, Zr, Ti.
8. according to the method for claim 1, it is characterised in that: the property for the Y molecular sieve that step (3) introduces is as follows: SiO2/
Al2O3Weight ratio be 9~20, cell parameter be 2.380~2.423nm, relative crystallinity > 100%, specific surface area be 750~
950 m2/ g, infrared acidity are 0.1~0.3mmol/g.
9. according to the method for claim 1, it is characterised in that: the weight ratio of macromolecular polyethylene glycol and Y molecular sieve is 1:
10 ~ 1:100；The molecular weight of polyethylene glycol is 1000 ~ 10000.
10. according to method described in claim 1 or 9, it is characterised in that: Y molecular sieve is ground with macromolecular polyethylene glycol through mixing
Honed journey is as follows: macromolecular polyethylene glycol being dissolved in water, Y molecular sieve is added, slurries is made, then in mortar or colloid mill
In grind 10~120min repeatedly.
11. according to the method for claim 1, it is characterised in that: in step (4), dry and roasting condition is as follows: 50 ~
120 DEG C drying 2.0 ~ 6.0 hours, 450 ~ 600 DEG C roast 3.0 ~ 6.0 hours.
12. according to the method for claim 1, it is characterised in that: on the basis of the weight of hydrocracking catalyst, tungsten oxide
Content with nickel oxide is 15% ~ 50%, and the content of magnesia is 3%~10%, and the content of amorphous silica-alumina is 20% ~ 80%, Y points
The content of son sieve is 5% ~ 35%.
13. according to method described in claim 1 or 12, it is characterised in that: in the hydrocracking catalyst, W and Ni's
Molar ratio is 1:10 ~ 10:1.
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| CN1253988A (en) * | 1998-11-18 | 2000-05-24 | 中国石油化工集团公司 | Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil |
| CN1766047A (en) * | 2004-10-28 | 2006-05-03 | 石油大学(北京) | Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method |
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| CN1766047A (en) * | 2004-10-28 | 2006-05-03 | 石油大学(北京) | Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method |
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