CN109926094A - A kind of hydrocracking catalyst and its preparation method - Google Patents
A kind of hydrocracking catalyst and its preparation method Download PDFInfo
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Abstract
The invention discloses a kind of hydrocracking catalyst and its preparation method, the hydrocracking catalyst includes acidic components, hydrogenation metal component, auxiliary agent and carrier, and acidic components are ammonium heteropoly acids.The preparation method of hydrocracking catalyst includes preparing catalyst precarsor, prepares carrier, supported acidic component and hydrogenation metal component to precursor modification.The catalyst that the method for the present invention obtains shows higher reactivity and liquid hydrocarbon-selective in the hydrocracking reaction for long chain alkane.
Description
Technical field
The invention belongs to petrochemical industry, be related to a kind of catalysis material and preparation method thereof, more particularly to one kind plus
Hydrogen Cracking catalyst and preparation method thereof.
Background technique
In petroleum refining industry, it is that feedstock oil exists that being hydrocracked, which is by the important process of mink cell focus production high-quality light-weight oil product,
High temperature, high pressure carry out adding hydrogen, desulfurization, denitrogenation, molecular skeleton rearrangement and cracking etc. chemical under the conditions of facing existing for hydrogen and catalyst
A kind of conversion process of reaction.Hydrocracking process can not only produce high grade light-end products, and liquid-phase product high income, skill
Art core is catalyst.Hydrocracking catalyst is a kind of bifunctional catalyst, has both acid function and hydrogenating function.US5,
536,687, the acid function of hydrocracking catalyst involved in US5,447,623 and EP0028938A1 is mainly by dividing
Son sieve provides, and hydrogenation component selects Mo-Ni or W-Ni.Catalyst zeolite containing Y 20%~40% involved by CN1389545A,
Phosphorus heteropoly tungstic acid or silicotungstic heteropolyacid 5%~20%, nickel oxide 5%~10%, aluminium oxide 40%~60%.Above-mentioned is adding containing molecular sieve
Hydrogen Cracking catalyst has acid strong, a big advantage of specific surface, but the disadvantage is that molecular sieve bore diameter is small, so as to cause reactant with
Product diffusional resistance increases, and the probability of second pyrolysis reaction increases.
CN1927461A discloses a kind of hydrocracking catalyst containing heteropoly acid, and heteropoly acid can be phosphotungstic acid or silicon tungsten
Acid, content are 40%~60%, and hydrogenation component (in terms of simple substance) preferably 5%~10%, surplus is carrier.Nothing is selected when preparation according to the ratio
Machine heat proof material particulate vector prepares the aqueous metal salt of hydrogenation component, impregnated carrier as catalyst carrier；Liquid is consolidated point
Solids drying from after, roasting；Heteropoly acid aqueous solution is prepared, solids obtained is impregnated, stands, dry, roasting.This contains miscellaneous
The hydrocracking catalyst of polyacid have the advantages that it is acid by force and aperture is big, but the disadvantage is that phosphotungstic acid high water solubility, use
A possibility that being relatively easy to run off in the process, and since the catalyst has highly acid, increasing second pyrolysis reaction.
CN201110350796.X discloses hydrocracking catalyst and preparation method thereof.The catalyst includes acid group
Point, hydrogenation component and carrier, acidic components are heteropoly acid alkali metal salt, and hydrogenation component is nickel, and carrier is silica；Catalyst is each
Content is acidic components 10%~20% to component by mass percentage, and hydrogenation component 3%~8%, surplus is carrier.This method is
Catalyst carrier is prepared using sol-gal process, and introduces hydrogenation metal component and alkali metal salt in carrier preparation process, it will
Carrier immerses heteropoly acid solution, up to catalyst after drying.The invention catalyst, heteropolyacid salt is evenly dispersed in the carrier, by
Acid weaker in it, content is lower, shows high liquid hydrocarbon-selective, but activity is relatively low.
CN201110350795.5 discloses a kind of hydrocracking catalyst and preparation method thereof.It is acid in the catalyst
Group is divided into silicotungstate, and hydrogenation metal component is nickel, and carrier is silica.This method is the introducing silicon tungsten in carrier preparation process
Hydrochlorate, silicotungstate is evenly dispersed in the carrier, and catalyst has preferable catalytic performance.But loaded in catalyst duct
Silicotungstate can make a part of product that second pyrolysis reaction occur, and reduce the selectivity of catalyst, influence target product yield.
Summary of the invention
It is in the prior art there are aiming at the problem that, it is an object of the present invention to provide a kind of hydrocracking catalyst and its preparations
Method.The catalyst of the method for the present invention preparation shows higher reaction and lives in the hydrocracking reaction for long chain alkane
Property and liquid hydrocarbon-selective.
First aspect present invention provides a kind of preparation method of hydrocracking catalyst, and the preparation method includes in following
Hold:
(1) it is prepared with compound, phosphorus-containing compound and water containing hydrogenation metal component water-soluble containing hydrogenation metal component and auxiliary agent P
Liquid；
(2) boehmite and water are mixed to form suspension；
(3) aqueous solution that step (1) obtains, template are mixed with heteropoly acid with the suspension that step (2) obtains；
(4) mixed solution that step (3) obtains is stirred at 60~90 DEG C to solution and is evaporated, through dry and roasting, be made and urge
Agent precursor A；
(5) processing is modified using the catalyst precarsor A that auxiliary agent A obtains step (4), obtains catalyst precarsor B；
(6) the catalyst precarsor B that step (5) obtains is added in auxiliary agent B, is separated by solid-liquid separation after mixing, will obtained
Solid phase stood at -50 DEG C~0 DEG C, preferably -30~0 DEG C；
(7) aqueous solutions of organic acids is mixed with the material that step (6) obtains, is separated by solid-liquid separation after mixing；
(8) alkaline solution containing ammonium is mixed with the solid-phase material that step (7) obtains, is separated by solid-liquid separation after mixing；
(9) heteropoly acid aqueous solution is mixed with the solid-phase material that step (8) obtains, is separated by solid-liquid separation after mixing, separated
Obtained solid phase obtains catalyst after drying, roasting.
In preparation method of the present invention, the compound containing hydrogenation metal component described in step (1) is containing vib metals
And/or the compound of group VIII metal, the compound containing vib metals can be molybdate compound, tungstenic chemical combination
One or more of object, the compound of the metal containing group VIII are cobalt compound, nickel compound containing, iron containing compounds
One or more of.The molybdate compound can be molybdenum oxide and/or ammonium heptamolybdate；The cobalt compound is alkali formula carbon
Sour cobalt and/or cobalt nitrate.
In preparation method of the present invention, the compound containing hydrogenation metal component described in step (1) is preferably molybdate compound
And cobalt compound.The molybdate compound can be molybdenum oxide and/or ammonium heptamolybdate；The cobalt compound is basic carbonate
Cobalt and/or cobalt nitrate.
In preparation method of the present invention, phosphorus-containing compound described in step (1) can be phosphoric acid, ammonium dihydrogen phosphate, phosphoric acid one
One or more of hydrogen ammonium.
In preparation method of the present invention, hydrogenation metal in the aqueous solution containing hydrogenation metal component and auxiliary agent P described in step (1)
The concentration of component is 0.03~0.3g/mL(in terms of hydrogenation metal oxide), the concentration of auxiliary agent P is 0.002~0.03 g/mL.
It can be prepared using the existing method in this field.
In preparation method of the present invention, the mass ratio of water described in step (2) and boehmite is 3~10.It is described quasi-
Boehmite can be used conventional method and be made, such as Alchlor process, aluminum sulfate method, carbonizatin method.
In preparation method of the present invention, template described in step (3) is dodecyl trimethyl ammonium bromide, dodecyl
Trimethyl ammonium chloride, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide,
One of octadecyltrimethylammonium chloride, hexamethylenetetramine are a variety of, the molar ratio of the template and aluminium oxide
It is 0.2~0.5.
In preparation method of the present invention, heteropoly acid described in step (3) and step (9) is phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid
One of or it is a variety of.The molar ratio that heteropoly acid is introduced in step (3) and step (9) is 4:1~1:4.
In preparation method of the present invention, drying temperature described in step (4) be 90~120 DEG C, drying time be 5.0~
10.0h；The maturing temperature is 400~550 DEG C, and calcining time is 2.0~6.0h.
In preparation method of the present invention, molding catalyst precarsor can be made in catalyst precarsor A described in step (4),
It is also possible to be not required to molding catalyst precarsor, those skilled in the art determine according to selected technique.Molding catalysis
Agent precursor can be formed using existing conventional molding techniques, such as extruded moulding, compression molding etc., and shape can be item
Shape, spherical shape, sheet etc..In forming process, it can according to need addition binder and shaping assistant, binder generally use small
Porous aluminum oxide.Shaping assistant such as peptizing agent, extrusion aid etc..
In preparation method of the present invention, modification process described in step (5) is as follows:
(5.1) auxiliary agent A is mixed with organic solvent, obtains solution I after mixing；
(5.2) alumina support is mixed with solution I, is reacted after mixing, then through being dried to obtain catalyst precarsor
B。
In step (5.1), the auxiliary agent A is octadecyl trimethoxysilane, hexadecyl trimethoxy silane, ten
One of dialkyl group trimethoxy silane, octadecyl trichlorosilane alkane, hexadecyl trichlorosilane, dodecyltrichlorosilane
Or it is several.
In step (5.1), the organic solvent be one or more of benzene, toluene, hexamethylene, wherein auxiliary agent A with
The mass ratio of organic solvent is 1:1~1:50.
In step (5.2), the reaction temperature is 40~60 DEG C, and the reaction time is 1.0~5.0h；The drying temperature
It is 70~90 DEG C, the time is 3.0~12.0h.
In preparation method of the present invention, auxiliary agent B described in step (6) is diesel oil, and the condensation point of the diesel oil is -40~20
DEG C, preferably -40~0 DEG C, further preferably -30~0 DEG C, the diesel oil can be straight-run diesel oil, hydrogenated diesel oil, coking bavin
Oil, one of catalytic diesel oil or a variety of, it is preferred to use hydrogenated diesel oil, specifically can use commercial goods diesel oil, as 5# diesel oil,
One of 0# diesel oil, -10# diesel oil, -20# diesel oil, -35# diesel oil are a variety of, and the volume ratio of the auxiliary agent B and aluminium oxide is 1
~4:1, preferably 1~2:1.
In preparation method of the present invention, organic acid described in step (7) be one of citric acid, tartaric acid, malic acid or
It is a variety of；The mass ratio of the organic acid and aluminium oxide is 0.1~1.5.
In preparation method of the present invention, the alkaline solution containing ammonium described in step (8) is ammonium hydroxide, sal volatile, carbonic acid
One of hydrogen ammonium salt solution is a variety of, and the dosage of the alkaline solution containing ammonium is excessive.
In preparation method of the present invention, drying described in step (9) carries out under vacuum, and relative degree of vacuum is -0.1MPa, does
Dry temperature be 90~120 DEG C, drying time be 3.0~12.0h, maturing temperature be 300~550 DEG C, calcining time be 2.0~
6.0h。
Second aspect of the present invention provides a kind of hydrocracking catalyst prepared using the above method, and described be hydrocracked is urged
Agent includes acidic components, hydrogenation metal component, auxiliary agent and carrier, and acidic components are ammonium heteropoly acids, and hydrogenation metal component is
One or more of vib metals and/or group VIII metal, P are auxiliary agent, and carrier is that aluminium oxide and silica are compound
Carrier, on the basis of the weight of catalyst, the contents of acidic components is 30%~40%, the content of hydrogenation metal component is 6%~
25%, auxiliary agent content is 1.0%~4.6%, and the content of carrier is 30.4%~63.0%.
In hydrocracking catalyst of the present invention, in complex carrier Silica-coated aluminium oxide, the weight of silica
Account for the 3%~15% of carrying alumina body weight.
In hydrocracking catalyst of the present invention, the specific surface area of the hydrocracking catalyst is 130~220m2/ g, hole
Holding is 0.3~0.5mL/g, and average pore diameter is 6.0~11.0nm.
In hydrocracking catalyst of the present invention, ammonium heteropoly acids are distributed in containing in catalyst center to 3/4 radius
Amount is the 11.4wt%~45.0wt%, preferably 18.8wt%~37.5wt% of total content；3/4 radius is distributed in catalyst appearance
The content in face is the 55.0wt%~88.6wt%, preferably 62.5wt%~81.2wt% of total content.
In hydrocracking catalyst of the present invention, the catalyst acid content is in the heart to 3/4 radius in the catalyst
It is uniformly distributed, acid content obviously increases within the scope of 3/4 radius to catalyst external surface, and 3/4 radius is to catalyst external surface
The ratio that the odds ratio catalyst center that acid content accounts for total acid content in range accounts for total acid content to the acid content in 3/4 radius is high
8.0wt%~75.0wt%, preferably 23.0~60.0wt%.
In hydrocracking catalyst of the present invention, heteropolyacid salt molecular formula is Hm(NH4)nYX12O40, wherein X represents W or Mo, Y
Represent Si or P；When Y represents Si, m+n=4, n value is 0.1~1.0；When Y represents P, m+n=3, n value is 0.1~1.0.
Compared with prior art, hydrocracking catalyst of the present invention and preparation method thereof has the advantages that
1, hydrocracking catalyst of the present invention has the advantages that outer surface acidity constituent content is high and utilization rate is high, described to add
Hydrogen Cracking catalyst improves catalyst external surface acidity while guaranteeing catalytic inner acidity, it is made to have high live
While property, selectivity with higher.
It 2,, not only can be with accelerating auxiliaries by introducing auxiliary agent A in the preparation method of hydrocracking catalyst of the present invention
Interaction between B and carrier, and realize the purpose being modified to alumina support simultaneously, in auxiliary agent A and auxiliary agent B
Under collective effect, it is possible to reduce a possibility that second pyrolysis occurred in catalyst duct reacts avoids generating excessively low
Carbon hydrocarbon.But also the ammonium heteropoly acids of subsequent load can be made to be distributed on the surface of the carrier, make major part heteropoly acid ammonium in this way
Salt is dispersed in carrier surface, and smaller portions ammonium heteropoly acids are dispersed in carrier duct, so that the catalyst acid content of preparation exists
It is evenly distributed in center to 3/4 radius, and acid content obviously increases within the scope of 3/4 radius to catalyst external surface,
Acid content accounts in the odds ratio catalyst center to 3/4 radius of total acid content out of 3/4 radius to catalyst external surface
Acid content account for the high 23.0wt%~60.0wt% of ratio of total acid content.
3, in the preparation method of hydrocracking catalyst of the present invention, the addition of the agent of class template containing ammonium can not only can be mentioned
The specific surface and Kong Rong of high-alumina can also be acted on heteropoly acid, generate heteropolyacid salt, while avoiding the strong acid of heteropoly acid
Property is to alumina pore structural damage.
4, in the preparation method of hydrocracking catalyst of the present invention, modification of the auxiliary agent A to carrier makes alumina support
Outer surface coated silica can reduce the interaction between the ammonium heteropoly acids of generation and aluminium oxide, improve catalysis
The acid amount of agent.
5, catalyst made from the method for the present invention is shown high anti-in the hydrocracking reaction for long chain alkane
Answer activity and higher liquid hydrocarbon-selective.
Specific embodiment
Below by embodiment, the present invention is described further, and reaction hydrocarbon raw material used in embodiment is to contain 525
The n-decane solution of μ g/g thiophene and 170 μ g/g pyridines.In the present invention, wt% is mass fraction.
Specific surface area, Kong Rong are measured using low temperature liquid nitrogen physisorphtion in the present invention, specifically use Merck & Co., Inc, the U.S.
The nitrogen absorption under low temperature instrument of ASAP2420 model measures；Detailed process: a small amount of sample is taken to be vacuum-treated 3~4h at 300 DEG C, most
Product is placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) afterwards and carries out nitrogen suction-desorption test.Wherein surface area is obtained according to BET equation
It arrives, pore-size distribution is obtained according to BJH model.SEM(scanning electron microscope) specifically using the JSM- of JEOL company, Japan production
The SEM(scanning electron microscope of 7500F type), it is equipped with EDAX-EDS, acceleration voltage: 20Kv, operating distance: 8mm, resolution ratio:
1nm。
Hydrogenation cracking activity indicates by the conversion ratio of n-decane, selectivity by " in product containing 5 carbon atoms and 5 with
The alkane molal quantity of upper carbon atom is divided by product total mole number " it indicates, it is denoted as C5 +Selectivity.This is because in general plus hydrogen
In process, it is desirable to which a pyrolysis product is more and second pyrolysis product is few, when being reaction hydrocarbon raw material with n-decane, in product
Alkane containing 5 carbon atoms and 5 or more carbon atom is all a pyrolysis product, so C5 +Selectivity characterizes one in product
The relative quantity of secondary pyrolysis product.
Embodiment 1
(1) preparation of Mo-Co-P aqueous solution:
By 2.3g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 6.2g molybdenum trioxide and 2.3g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.06g/mL, Co2O3Concentration be 0.012g/mL, the concentration of P is 0.006g/mL.
(2) preparation of catalyst:
53.4g boehmite (butt 0.85) is added in 300g water, forms suspension after mashing；By 100mL Mo-Co-
P aqueous solution, 34.9g Cetyltrimethylammonium bromide and 31.4g phosphotungstic acid are sequentially added in suspension, at 70 DEG C
Lower stirring to solution is evaporated, and in 110 DEG C of dry 8.0h, then in 400 DEG C of 3.0 h of roasting, catalyst precarsor A is made；Then plus
Enter in the cyclohexane solution for containing 36.3g dodecyltrimethoxysilane to 150mL, react 3.0h at 50 DEG C, at 70 DEG C
Dry 8h, obtains catalyst precarsor B；It is then added in 120mL5# diesel oil, is filtered after impregnating 30min, obtained material is placed in
In 0 DEG C of low-temp reaction bath, the aqueous solution that 120mL contains 22.7g citric acid is then added and falls solution after impregnating 30min
Out, the sal volatile that 120mL mass fraction is 30% is then added and impregnates 5min, solution is poured out, 100mL is then added and contains
There is the aqueous solution of 7.9g phosphotungstic acid, is filtered after impregnating 5min, by obtained solid in the case where relative degree of vacuum is -0.1MPa, 110 DEG C
Then in 400 DEG C of roasting 3.0h catalyst is made, wherein MoO in dry 8.0h3Content is 6wt%, Co2O3Content is 1.2wt%,
P content is 0.6wt%, (NH4)0.7H2.3PW12O40Content is 38wt%, and the weight of silica accounts for the 15% of carrying alumina body weight.
The physico-chemical property of catalyst is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(4) evaluating catalyst:
After 0.5g catalyst to be packed into the isothermal section among reaction tube, it is passed through hydrogen, reaction system steps up pressure extremely
2.0MPa is passed through the CS of % containing 2wt after inspection is air tight2N-heptane solution, reaction system is warming up to 320 DEG C of vulcanization 3h,
After cut the n-decane liquid containing 525 μ g/g thiophene and 170 μ g/g pyridines, reaction system is then warming up to 400 DEG C,
In hydrogen volume air speed 1500h-1Under, mass space velocity 3.0h-1, start to acquire sample after reacting 1h, detect catalyst anti-
Hydrogenation cracking activity and selectivity under the conditions of answering, the results are shown in Table 3.
Embodiment 2
(1) preparation of Mo-Co-P aqueous solution:
By 4.6g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 12.4g molybdenum trioxide and 5.8g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.12g/mL, Co2O3Concentration be 0.03g/mL, the concentration of P is 0.012g/mL.
(2) preparation of catalyst:
52.1g boehmite (butt 0.85) is added in 300g water, forms suspension after mashing；By 100mL Mo-Co-
P aqueous solution, 47.5g cetyl trimethylammonium bromide and 17.6g phosphotungstic acid are sequentially added in suspension, at 70 DEG C
Lower stirring to solution is evaporated, and in 110 DEG C of dry 8.0h, then in 470 DEG C of 3.0 h of roasting, catalyst precarsor A is made；Then plus
Enter in the cyclohexane solution for containing 21.1g hexadecyl trimethoxy silane to 150mL, react 3.0h at 50 DEG C, at 70 DEG C
Dry 8h, obtains catalyst precarsor B；It is then added in 120mL0# diesel oil, is filtered after impregnating 30min, obtained material is set
In -10 DEG C of low-temp reaction bath, the aqueous solution that 120mL contains 44.3g citric acid is then added, after impregnating 30min, by solution
It pours out, the sal volatile that 120mL mass fraction is 30% is then added and impregnates 5min, solution is poured out, 100mL is then added
Aqueous solution containing 17.6g phosphotungstic acid filters after impregnating 5min, by obtained solid in the case where relative degree of vacuum is -0.1MPa,
Then in 470 DEG C of roasting 3.0h catalyst is made, wherein MoO in 110 DEG C of dry 8.0h3Content is 12wt%, Co2O3Content is
3.0wt%, P content 1.2wt%, (NH4)0.5H2.5PW12O40Content is 34wt%, and the weight of silica accounts for carrying alumina weight
The 8% of amount.The physico-chemical property of catalyst is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(4) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Embodiment 3
(1) preparation of Mo-Co-P aqueous solution:
By 6.9g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 6.2g molybdenum trioxide and 8.6g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.18g/mL, Co2O3Concentration be 0.045g/mL, the concentration of P is 0.018g/mL.
(2) preparation of catalyst:
47.2g boehmite (butt 0.85) is added in 300g water, forms suspension after mashing；By 100mL Mo-Co-
P aqueous solution, 60.6g dodecyl trimethyl ammonium bromide and 6.7g phosphotungstic acid are sequentially added in suspension, at 70 DEG C
Lower stirring to solution is evaporated, and in 110 DEG C of dry 8.0h, then in 500 DEG C of 3.0 h of roasting, catalyst precarsor A is made；Then plus
Enter in the cyclohexane solution for containing 7.0g octadecyl trimethoxysilane to 150mL, reacts 3.0h at 50 DEG C, it is dry at 70 DEG C
Dry 8h obtains catalyst precarsor B；It is then added in 120mL-10# diesel oil, is filtered after impregnating 30min, obtained material is set
In -20 DEG C of low-temp reaction bath, the aqueous solution that 120mL contains 60.2g citric acid is then added, after impregnating 30min, by solution
It pours out, the sal volatile that 120mL mass fraction is 30% is then added and impregnates 5min, solution is poured out, 100mL is then added
Aqueous solution containing 26.5g phosphotungstic acid filters after impregnating 5min, by obtained solid in the case where relative degree of vacuum is -0.1MPa,
Then in 500 DEG C of roasting 3.0h catalyst is made, wherein MoO in 110 DEG C of dry 8.0h3Content is 18wt%, Co2O3Content is
4.5wt%, P content 1.8wt%, (NH4)0.1H2.9PW12O40Content is 32wt%, and the weight of silica accounts for carrying alumina weight
The 3% of amount.The physico-chemical property of catalyst is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(4) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Embodiment 4
(1) preparation of catalyst:
In embodiment 3, phosphotungstic acid is changed to silico-tungstic acid, it is 20% that the sal volatile that mass fraction is 30%, which is changed to mass fraction,
Ammonium hydroxide, catalyst is made, wherein MoO with embodiment 3 in remaining3Content is 18wt%, Co2O3Content is 4.5wt%, and P content is
1.8wt%, (NH4)0.1H3.9SiW12O40Content is 32wt%, and the weight of silica accounts for the 3% of carrying alumina body weight.Catalyst
Physico-chemical property be shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Embodiment 5
In embodiment 3, n-decane solution is changed to hexadecane solution, remaining evaluation is with embodiment 3, and catalyst is in reaction item
Hydrogenation cracking activity and selectivity under part, the results are shown in Table 3.
Comparative example 1
(1) preparation of catalyst:
In embodiment 3,48.6g boehmite (butt 0.85) is added in 300g water, forms suspension after mashing；It will
100mL Mo-Co-P aqueous solution, 62.4g dodecyl trimethyl ammonium bromide and 6.7g phosphotungstic acid are sequentially added to suspended
In liquid, stirring to solution is evaporated at 70 DEG C, in 110 DEG C of dry 8.0h, then in 500 DEG C of 3.0 h of roasting, before catalyst is made
Body A；It is then added to 120mL to contain in the aqueous solution of 62.0g citric acid, after impregnating 30min, solution is poured out, is then added
The sal volatile that 120mL mass fraction is 30% impregnates 5min, and solution is poured out, and 100mL is then added and contains 26.5g phosphorus tungsten
The aqueous solution of acid filters after impregnating 5min, by obtained solid in the case where relative degree of vacuum is -0.1MPa, 110 DEG C of dry 8.0h,
Then in 500 DEG C of roasting 3.0h, catalyst is made, wherein MoO3Content is 18wt%, Co2O3Content is 4.5wt%, and P content is
1.8wt%, (NH4)0.1H2.9PW12O40Content is 32wt%.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Comparative example 2
It is substantially the same manner as Example 3, the difference is that auxiliary agent A is not used to be modified catalyst precarsor A.
(1) preparation of catalyst:
In embodiment 3,48.6g boehmite (butt 0.85) is added in 300g water, forms suspension after mashing；It will
100mL Mo-Co-P aqueous solution, 62.4g dodecyl trimethyl ammonium bromide and 6.7g phosphotungstic acid are sequentially added to suspended
In liquid, stirring to solution is evaporated at 70 DEG C, in 110 DEG C of dry 8.0h, then in 500 DEG C of roasting 3.0h, before catalyst is made
Body A；It is added to catalyst precarsor A in 120mL-10# diesel oil, is filtered after impregnating 30min, obtained material is placed in -20 DEG C
In low-temp reaction bath, the aqueous solution that 120mL contains 60.2g citric acid is then added and is poured out solution, then after impregnating 30min
The sal volatile that 120mL mass fraction is 30% is added and impregnates 5min, solution is poured out, 100mL is then added and contains 26.5g
The aqueous solution of phosphotungstic acid filters after impregnating 5min, by obtained solid in the case where relative degree of vacuum is -0.1MPa, 110 DEG C of dryings
Then in 500 DEG C of 3.0 h of roasting catalyst is made, wherein MoO in 8.0h3Content is 18wt%, Co2O3Content is 4.5wt%, P
Content is 2.0wt%, (NH4)0.1H2.9PW12O40Content is 32wt%.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Modification of the auxiliary agent A to catalyst, on the one hand can weaken the acidity of carrier itself, on the other hand can weaken carrier
Interaction between phosphotungstic acid amine salt reduces the salt acidic loss of heteropoly acid ammonium, so the modification of auxiliary agent A plays weakening
It is acid in catalyst duct, improve the effect of catalyst external surface acidity.Compared with Example 3,2 catalyst of comparative example does not use
Auxiliary agent A is modified, acid in catalyst duct not to be weakened, and outer surface acidity, because ammonium heteropoly acids and carrier interact
Weakened.Therefore, the conversion ratio of catalyst and selectivity all decrease.
Comparative example 3
It is substantially the same manner as Example 3, the difference is that auxiliary agent B is not used to be modified catalyst precarsor B.
(1) preparation of catalyst:
Catalyst precarsor B is added to 120mL to contain in the aqueous solution of 60.2g citric acid, after impregnating 30min, solution is poured out,
Then the sal volatile that 120mL mass fraction is 30% is added and impregnates 5min, solution is poured out, 100mL is then added and contains
The aqueous solution of 26.5g phosphotungstic acid filters after impregnating 5min, by obtained solid in the case where relative degree of vacuum is -0.1MPa, 110 DEG C
Dry 8.0h, then in 500 DEG C of 3.0 h of roasting, catalyst is made, wherein MoO3Content is 18wt%, Co2O3Content is
4.5wt%, P content 1.8wt%, (NH4)0.1H2.9PW12O40Content is 32wt%, and the weight of silica accounts for carrying alumina weight
The 3% of amount.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
The physico-chemical property of 1 catalyst of table
2 catalyst different location heteropoly acid ammonium salt content of table accounts for the percentage (wt%) of total content
The hydrogenation cracking activity and selectivity of 3 catalyst of table
Claims (30)
1. a kind of preparation method of hydrocracking catalyst, the preparation method includes following content:
(1) it is prepared with compound, phosphorus-containing compound and water containing hydrogenation metal component water-soluble containing hydrogenation metal component and auxiliary agent P
Liquid；
(2) boehmite and water are mixed to form suspension；
(3) aqueous solution that step (1) obtains, template are mixed with heteropoly acid with the suspension that step (2) obtains；
(4) mixed solution that step (3) obtains is stirred at 60~90 DEG C to solution and is evaporated, through dry and roasting, be made and urge
Agent precursor A；
(5) processing is modified using the catalyst precarsor A that auxiliary agent A obtains step (4), obtains catalyst precarsor B；
(6) the catalyst precarsor B that step (5) obtains is added in auxiliary agent B, is separated by solid-liquid separation after mixing, will obtained
Solid phase stood at -50 DEG C~0 DEG C, preferably -30~0 DEG C；
(7) aqueous solutions of organic acids is mixed with the material that step (6) obtains, is separated by solid-liquid separation after mixing；
(8) alkaline solution containing ammonium is mixed with the solid-phase material that step (7) obtains, is separated by solid-liquid separation after mixing；
(9) heteropoly acid aqueous solution is mixed with the solid-phase material that step (8) obtains, is separated by solid-liquid separation after mixing, separated
Obtained solid phase obtains catalyst after drying, roasting.
2. preparation method described in accordance with the claim 1, it is characterised in that: the change containing hydrogenation metal component described in step (1)
Conjunction object is the compound containing vib metals and/or group VIII metal.
3. preparation method described in accordance with the claim 1, it is characterised in that: the compound containing vib metals is containing molybdenum
One or more of compound, Tungstenic compound, the compound of the metal containing group VIII are cobalt compound, nickeliferousization
Close one or more of object, iron containing compounds.
4. preparation method described in accordance with the claim 1, it is characterised in that: the change containing hydrogenation metal component described in step (1)
Closing object is preferably molybdate compound and cobalt compound.
5. according to preparation method described in claim 3 or 4, it is characterised in that: the molybdate compound is molybdenum oxide and/or seven
Ammonium molybdate；The cobalt compound is basic cobaltous carbonate and/or cobalt nitrate.
6. preparation method described in accordance with the claim 1, it is characterised in that: phosphorus-containing compound described in step (1) is phosphoric acid, phosphorus
One or more of acid dihydride ammonium, monoammonium phosphate.
7. preparation method described in accordance with the claim 1, it is characterised in that: contain hydrogenation metal component described in step (1) and help
The concentration of hydrogenation metal component is 0.03~0.3g/mL in the aqueous solution of agent P, and the concentration of auxiliary agent P is 0.002~0.03 g/mL.
8. preparation method described in accordance with the claim 1, it is characterised in that: water described in step (2) and boehmite
Mass ratio is 3~10.
9. preparation method described in accordance with the claim 1, it is characterised in that: template described in step (3) is dodecyl
Trimethylammonium bromide, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride,
One of Cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride, hexamethylenetetramine are a variety of.
10. preparation method described in accordance with the claim 1, it is characterised in that: template described in step (3) and aluminium oxide
Molar ratio is 0.2~0.5.
11. preparation method described in accordance with the claim 1, it is characterised in that: heteropoly acid described in step (3) and step (9)
For one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
12. preparation method described in accordance with the claim 1, it is characterised in that: drying temperature described in step (4) is 90~120
DEG C, drying time is 5.0~10.0h；The maturing temperature is 400~550 DEG C, and calcining time is 2.0~6.0h.
13. preparation method described in accordance with the claim 1, it is characterised in that: modification process described in step (5) is such as
Under:
(5.1) auxiliary agent A is mixed with organic solvent, obtains solution I after mixing；
(5.2) alumina support is mixed with solution I, is reacted after mixing, then through being dried to obtain catalyst precarsor
B。
14. preparation method according to claim 13, it is characterised in that: auxiliary agent A described in step (5.1) is octadecane
Base trimethoxy silane, hexadecyl trimethoxy silane, dodecyltrimethoxysilane, octadecyl trichlorosilane alkane, ten
One or more of six alkyltrichlorosilanes, dodecyltrichlorosilane.
15. preparation method according to claim 13, it is characterised in that: organic solvent described in step (5.1) be benzene,
One or more of toluene, hexamethylene.
16. preparation method according to claim 13, it is characterised in that: the mass ratio of auxiliary agent A and organic solvent be 1:1~
1:50。
17. preparation method according to claim 13, it is characterised in that: reaction temperature described in step (5.2) be 40~
60 DEG C, the reaction time is 1.0~5.0h；The drying temperature is 70~90 DEG C, and the time is 3.0~12.0h.
18. preparation method described in accordance with the claim 1, it is characterised in that: auxiliary agent B described in step (6) is diesel oil, described
The condensation point of diesel oil is -40~20 DEG C, preferably -40~0 DEG C, further preferably -30~0 DEG C.
19. preparation method according to claim 18, it is characterised in that: diesel oil described in step (6) is straight-run diesel oil, is added
Hydrogen diesel oil, coker gas oil, one of catalytic diesel oil or a variety of, it is preferred to use hydrogenated diesel oil.
20. preparation method according to claim 18, it is characterised in that: diesel oil described in step (6) uses commercial goods
Diesel oil, such as one of 5# diesel oil, 0# diesel oil, -10# diesel oil, -20# diesel oil, -35# diesel oil or a variety of.
21. preparation method described in accordance with the claim 1, it is characterised in that: the body of auxiliary agent B and aluminium oxide described in step (6)
Product is than being 1~4:1, preferably 1~2:1.
22. preparation method described in accordance with the claim 1, it is characterised in that: organic acid described in step (7) is citric acid, wine
One of stone acid, malic acid are a variety of；The mass ratio of the organic acid and aluminium oxide is 0.1~1.5.
23. preparation method described in accordance with the claim 1, it is characterised in that: the alkaline solution containing ammonium described in step (8) is
One of ammonium hydroxide, sal volatile, ammonium bicarbonate soln are a variety of.
24. preparation method described in accordance with the claim 1, it is characterised in that: drying described in step (9) carries out under vacuum,
Relative degree of vacuum be -0.1MPa, drying temperature be 90~120 DEG C, drying time be 3.0~12.0h, maturing temperature be 300~
550 DEG C, calcining time is 2.0~6.0h.
25. using the hydrocracking catalyst of any claim the method preparation in claim 1-24, described plus hydrogen is split
Changing catalyst includes acidic components, hydrogenation metal component, auxiliary agent and carrier, and acidic components are ammonium heteropoly acids, hydrogenation metal group
It is divided into one or more of vib metals and/or group VIII metal, P is auxiliary agent, and carrier is aluminium oxide and silica
Complex carrier, on the basis of the weight of catalyst, the content of acidic components is 30%~40%, and the content of hydrogenation metal component is 6%
~25%, auxiliary agent content is 1.0%~4.6%, and the content of carrier is 30.4%~63.0%.
26. according to the hydrocracking catalyst described in claim 25, it is characterised in that: Silica-coated in complex carrier
Aluminium oxide, the weight of silica account for the 3%~15% of carrying alumina body weight.
27. according to the hydrocracking catalyst described in claim 25, it is characterised in that: the ratio table of the hydrocracking catalyst
Area is 130~220m20.3~0.5mL/g of/g, Kong Rongwei, average pore diameter are 6.0~11.0nm.
28. according to the hydrocracking catalyst described in claim 25, it is characterised in that: ammonium heteropoly acids are distributed in the catalyst
The heart to the content in 3/4 radius be total content 11.4wt%~45.0wt%, preferably 18.8wt%~37.5wt%；Distribution
3/4 radius to catalyst external surface content be total content 55.0wt%~88.6wt%, preferably 62.5wt%~
81.2wt%。
29. according to the hydrocracking catalyst described in claim 25, it is characterised in that: the catalyst acid content is in catalyst
It being evenly distributed in center to 3/4 radius, acid content obviously increases within the scope of 3/4 radius to catalyst external surface, and
Acid content accounts in the odds ratio catalyst center to 3/4 radius of total acid content within the scope of 3/4 radius to catalyst external surface
Acid content accounts for the ratio high 8.0wt%~75.0wt%, preferably 23.0~60.0wt% of total acid content.
30. according to the hydrocracking catalyst described in claim 25, it is characterised in that: heteropolyacid salt molecular formula is Hm(NH4)nYX12O40, wherein X represents W or Mo, and Y represents Si or P；When Y represents Si, m+n=4, n value is 0.1~1.0；When Y represents P
When, m+n=3, n value is 0.1~1.0.
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