CN109926074A - Hydrocracking catalyst and preparation method thereof - Google Patents
Hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of hydrocracking catalyst and preparation method thereof, the hydrocracking catalyst includes acidic components, hydrogenation metal component and carrier, and acidic components are ammonium heteropoly acids.A kind of preparation method of above-mentioned hydrocracking catalyst is also provided, the method includes being modified to alumina support, then supported acidic component and active component.The catalyst that the method for the present invention obtains shows higher reactivity and high liquid hydrocarbon-selective in the hydrocracking reaction for long chain alkane.
Description
Technical field
The invention belongs to refining art, it is related to a kind of catalysis material and preparation method thereof, is urged more particularly to one kind plus hydrogen
Agent 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 to use
Sol-gal process prepares catalyst carrier, and hydrogenation metal component and alkali metal salt are introduced in carrier preparation process, by carrier
Heteropoly acid solution is immersed, up to catalyst after drying.The invention catalyst, heteropolyacid salt is evenly dispersed in the carrier, due to it
Acid weaker, 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
Aiming at the problems existing in the prior art, it is an object of the present invention to provide a kind of hydrocracking catalyst and its preparations
Method.The reactivity with higher of catalyst made from the method for the present invention and high 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) processing is modified to alumina support using auxiliary agent A, obtains catalyst precarsor A；
(3) the catalyst precarsor A that step (2) obtains is mixed with auxiliary agent B, is separated by solid-liquid separation after mixing, by what is obtained
Solid phase is stood at -50 DEG C~0 DEG C, preferably -30~0 DEG C；
(4) aqueous solutions of organic acids is mixed with the material that step (3) obtains, is separated by solid-liquid separation after mixing；
(5) alkaline solution containing ammonium is mixed with the solid-phase material that step (4) obtains, is separated by solid-liquid separation after mixing；
(6) heteropoly acid aqueous solution is mixed with the solid-phase material that step (5) obtains, is separated by solid-liquid separation after mixing, separated
Obtained solid phase is dried to obtain catalyst precarsor B；
(7) aqueous solution that step (1) obtains is mixed with catalyst precarsor B, is urged after drying, roasting after being uniformly mixed
Agent.
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 the metal containing group VIII, the compound containing vib metals can be molybdate compound, contain tungsten
One or more of object is closed, the compound of the metal containing group VIII is cobalt compound, nickel compound containing, iron content chemical combination
One or more of object.The molybdate compound can be molybdenum oxide and/or ammonium heptamolybdate；The cobalt compound is alkali formula
Cobalt carbonate 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.
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, alumina support described in step (2) generallys use ball-aluminium oxide, alumina support
It can be obtained by boehmite through molding, drying and roasting.The boehmite can be used conventional method and be made, such as chlorine
Change aluminium method, aluminum sulfate method, carbonizatin method etc..
In preparation method of the present invention, carrying alumina volume property described in step (2) is as follows: 0.6~0.9mL/g of Kong Rongwei,
Specific surface area is 160~320m2/ g, particle diameter 0.1mm~1.2mm.
In preparation method of the present invention, modification process described in step (2) is as follows:
(2.1) auxiliary agent A is mixed with organic solvent, obtains solution I after mixing；
(2.2) alumina support is mixed with solution I, is reacted after mixing, then through being dried to obtain catalyst precarsor
A。
In step (2.1), 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 (2.1), 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 (2.2), 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 (3) 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 (4) 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 (5) is ammonium hydroxide, sal volatile, bicarbonate
One of 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, heteropoly acid described in step (6) be one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or
It is a variety of.
In preparation method of the present invention, drying temperature described in step (6) be 90~120 DEG C, drying time be 5.0~
10.0h。
In preparation method of the present invention, the preferably high-temperature process in a nitrogen atmosphere of isolated solid phase described in step (6),
Catalyst precarsor B is obtained after processing, the treatment temperature is 300~400 DEG C, and the time is 2.0~5.0h.
In preparation method of the present invention, drying described in step (7) temperature be 60~120 DEG C, drying time be 3.0~
12.0h；The drying is carried out preferably by the way of Two stage dryer, and wherein first segment drying temperature is 60~90 DEG C, second segment
Drying temperature is 90~120 DEG C；The maturing temperature is 400~550 DEG C, and calcining time is 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, wherein Silica-coated aluminium oxide, the weight of silica account for the 3%~15% of carrying alumina body weight；With catalysis
On the basis of the weight of agent, the content of acidic components is 10%~30%, and the content of hydrogenation metal component is 6%~25%, auxiliary agent content
It is 1.0%~4.6%, the content of carrier is 40.4%~83.0%.
In hydrocracking catalyst of the present invention, the vib metals are generally Mo and/or W, and group VIII metal is general
For Ni and/or Co.
In hydrocracking catalyst of the present invention, the specific surface area of the hydrocracking catalyst is 140~280m2/ g, hole
Holding is 0.2~0.6mL/g, and average pore diameter is 5.0~10.0nm.
In hydrocracking catalyst of the present invention, the ammonium heteropoly acids are distributed in catalyst external surface to 30 μ m thick of center
Interior content accounts for 92wt%~100wt% of ammonium heteropoly acids total content, preferably 95wt%~98wt%.The catalyst acid content
85wt%~95wt% integrated distribution is in catalyst external surface into 30 μ m thick of center.
In hydrocracking catalyst of the present invention, the hydrogenation metal component is preferably Mo and Co, is with the weight of catalyst
Benchmark, MoO3Content is 5%~20%, Co2O3Content be 1%~5%.
In hydrocracking catalyst of the present invention, the ammonium heteropoly acids molecular formula is Hm(NH4)nYX12O40, wherein X is represented
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 acidic components distribution collection neutralization utilization rate is high, and described plus hydrogen is split
While changing the raising of catalyst surface acidity, the acidity in catalyst duct is reduced, highly selective feature is made it have.
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
It, can be to avoid when using the catalyst to carry out hydrogenation reaction under collective effect, two secondary fissures that raw material occurs in catalyst duct
It a possibility that solution reaction, avoids generating excessive lower carbon number hydrocarbons.But also it can guarantee that ammonium heteropoly acids are as much as possible and be supported on
Carrier outer surface, so that catalyst acid content 85wt%~95wt% integrated distribution of preparation is in catalyst external surface to 30 μm of center
In thickness.
3, in the preparation method of hydrocracking catalyst of the present invention, modification of the auxiliary agent A to carrier makes alumina support
On the one hand outer surface coated silica can reduce the interaction between the ammonium heteropoly acids of generation and aluminium oxide, drop
In low catalyst duct while acid amount, the acid amount of catalyst surface is improved.
4, in the preparation method of hydrocracking catalyst of the present invention, when preparing catalyst precarsor B, by nitrogen gas
High-temperature process under atmosphere can effectively prevent the strong interaction between metal component and carrier, and generation active component is avoided to form point
Spar phase is conducive to the vulcanization of the active component molybdenum cobalt of subsequent load, further increases the activity of catalyst.
5, catalyst made from the method for the present invention is shown higher in the hydrocracking reaction for long chain alkane
Reactivity and high 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 1.9g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 5.2g molybdenum trioxide and 1.9g 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 0.05g/mL, Co2O3Concentration be 0.01g/mL, the concentration of P is 0.005g/mL.
(2) preparation of catalyst:
By 80.4g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, it is spherical, particle diameter 0.4mm~
It 0.6mm) is added to 200mL to contain in the cyclohexane solution of 11.3g dodecyltrimethoxysilane, be reacted at 50 DEG C
3.0h obtains catalyst precarsor A in 70 DEG C of dry 8h；It is then added in 200mL5# diesel oil, filters, obtain after impregnating 30min
To material be placed in 0 DEG C low-temp reaction bath in, 150mL is then added and contains the aqueous solution of 40.2g citric acid, impregnates 30min
Afterwards, solution is poured out, the sal volatile that 150mL mass fraction is 30% is then added and impregnates 5min, solution is poured out, then
The aqueous solution that 100mL contains 10.4g phosphotungstic acid is added, is filtered after impregnating 5min, by 350 DEG C in a nitrogen atmosphere of obtained solid
High-temperature process 4.0h obtains catalyst precarsor B；Then 100mL Mo-Co-P aqueous solution is added, after mixing in 70 DEG C of dryings
4h then heats to 110 DEG C of dry 4h, then in 500 DEG C of roasting 3.0h, catalyst is made, wherein MoO3Content is 5wt%,
Co2O3Content is 1wt%, P content 0.5wt%, (NH4)0.1H2.9PW12O40Content is 10wt%, and the weight of silica accounts for oxidation
The 3% of alumina supporter weight.The physico-chemical property of catalyst is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst each point by SEM, the results showed that be distributed in catalyst external surface to 30 um of center thickness
Heteropoly acid ammonium salt content in degree is the 98wt% of total content.
(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 3 h of vulcanization,
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 is 2.5 h-1, start to acquire sample, detection catalysis after reacting 1 h
Agent hydrogenation cracking activity at reaction conditions and selectivity, the results are shown in Table 2.
Embodiment 2
(1) preparation of Mo-Co-P aqueous solution:
By 4.5g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 15.5g molybdenum trioxide and 5.7g 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 0.15g/mL, Co2O3Concentration be 0.03g/mL, the concentration of P is 0.012g/mL.
(2) preparation of catalyst:
By 53.4g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, it is spherical, particle diameter 0.4mm~
It 0.6mm) is added to 200mL to contain in the cyclohexane solution of 32.0g hexadecyl trimethoxy silane, be reacted at 50 DEG C
3.0h obtains catalyst precarsor A in 70 DEG C of dry 8h；It is then added in 150mL0# diesel oil, filters, obtain after impregnating 30min
To material be placed in -10 DEG C low-temp reaction bath in, 150mL is then added and contains the aqueous solution of 64.0g citric acid, dipping
After 30min, solution is poured out, the sal volatile that 150mL mass fraction is 30% is then added and impregnates 5min, solution is poured out,
Then the aqueous solution that 100mL contains 20.8g phosphotungstic acid is added, is filtered after impregnating 5min, in a nitrogen atmosphere by obtained solid
350 DEG C of high-temperature process 4.0h, obtain catalyst precarsor B；Then 100mL Mo-Co-P aqueous solution is added, after mixing 70
DEG C dry 4h, then heats to 110 DEG C of dry 4h, then in 470 DEG C of roasting 3.0h, obtained catalyst, and wherein MoO3Content is
15wt%, Co2O3Content is 3.0wt%, P content 1.2wt%, (NH4)0.5H2.5PW12O40Content is 20wt%, the weight of silica
Amount accounts for the 10% 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 each point by SEM, the results showed that be distributed in catalyst external surface to 30 um of center thickness
Heteropoly acid ammonium salt content in degree is the 97wt% of total content.
(4) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 2.
Embodiment 3
(1) preparation of Mo-Co-P aqueous solution:
By 7.6g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 20.7g molybdenum trioxide and 9.4g 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 0.2g/mL, Co2O3Concentration be 0.05g/mL, the concentration of P is 0.02g/mL.
(2) preparation of catalyst:
By 34.3g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, it is spherical, particle diameter 0.4mm~
It 0.6mm) is added to 150mL to contain in the cyclohexane solution of 35.7g octadecyl trimethoxysilane, be reacted at 50 DEG C
3.0h obtains catalyst precarsor A in 70 DEG C of dry 8h；It is then added in 150mL-10# diesel oil, is filtered after impregnating 30min,
Obtained material is placed in -20 DEG C of low-temp reaction bath, and the aqueous solution that 100mL contains 51.5g citric acid, dipping is then added
After 30min, solution is poured out, the sal volatile that 100mL mass fraction is 30% is then added and impregnates 5min, solution is poured out,
Then the aqueous solution that 100mL contains 31.1g phosphotungstic acid is added, is filtered after impregnating 5min, in a nitrogen atmosphere by obtained solid
350 DEG C of high-temperature process 4.0h, obtain catalyst precarsor B；Then 100mL Mo-Co-P aqueous solution is added, after mixing 70
DEG C dry 4h, then heats to 110 DEG C of dry 4h, then in 400 DEG C of roasting 3.0h, obtained catalyst, and wherein MoO3Content is
20wt%, Co2O3Content is 5wt%, P content 2wt%, (NH4)0.7H2.3PW12O40Content is 30wt%, 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 each point by SEM, the results showed that be distributed in catalyst external surface to 30 um of center thickness
Heteropoly acid ammonium salt content in degree is the 96wt% of total content.
(4) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 2.
Embodiment 4
(1) preparation of catalyst:
In embodiment 1, 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 1 in remaining3Content is 5wt%, Co2O3Content is 1wt%, and P content is
0.5wt%, (NH4)0.1H3.9SiW12O40Content is 10wt%, 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 each point by SEM, the results showed that be distributed in catalyst external surface to 30 um of center thickness
Heteropoly acid ammonium salt content in degree is the 98wt% of total content.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 2.
Embodiment 5
(1) preparation of catalyst:
In embodiment 1, it by the lower 350 DEG C of high-temperature process 4.0h of nitrogen atmosphere, is changed in the case where relative degree of vacuum is -0.1MPa, 110
DEG C dry 8.0h, with embodiment 1 catalyst is made, wherein MoO in remaining3Content is 5wt%, Co2O3Content is 1wt%, and P content is
0.5wt%, (NH4)0.1H2.9PW12O40Content is 10wt%, and the weight of silica accounts for the 3% of carrying alumina body weight.Catalyst
Physico-chemical property is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst each point by SEM, the results showed that be distributed in catalyst external surface to 30 um of center thickness
Heteropoly acid ammonium salt content in degree is the 98wt% of total content.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 2.
Embodiment 6
In embodiment 1, n-decane solution is changed to hexadecane solution, remaining evaluation is with embodiment 1, and catalyst is in reaction item
Hydrogenation cracking activity and selectivity under part, the results are shown in Table 2.
Comparative example 1
(1) preparation of catalyst:
In embodiment 1,82.9g alumina support is added to 150mL to contain in the aqueous solution of 41.5g citric acid, is impregnated
After 30min, solution is poured out, the sal volatile that 150mL mass fraction is 30% is then added, impregnates 5min, solution is fallen
Out, the aqueous solution that 100mL contains 10.4g phosphotungstic acid is then added, is filtered after impregnating 5min, by obtained solid in nitrogen atmosphere
Lower 350 DEG C of high-temperature process 4.0h, obtain catalyst precarsor A；Then 100mL Mo-Co-P aqueous solution is added, exists after mixing
70 DEG C of dry 4h then heat to 110 DEG C of dry 4h, and by obtained solid in 500 DEG C of roasting 3.0h, catalyst is made, wherein
MoO3Content is 5wt%, Co2O3Content is 1wt%, P content 0.5wt%, (NH4)0.1H2.9PW12O40Content is 10wt%.Catalyst
Physico-chemical property be shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst each point by SEM, the results showed that ammonium heteropoly acids are uniformly distributed on a catalyst
's.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 2.
Comparative example 2
It is substantially the same manner as Example 1, the difference is that without using auxiliary agent A dodecyltrimethoxysilane to alumina support
It is modified processing.
(1) preparation of catalyst:
In embodiment 1,82.9g alumina support is added in 200mL5# diesel oil, is filtered after impregnating 30min, obtained object
Material is placed in 0 DEG C of low-temp reaction bath, and the aqueous solution that then addition 150mL contains 41.5g citric acid will be molten after impregnating 30min
Liquid is poured out, and the sal volatile that 150mL mass fraction is 30% is then added and impregnates 5min, solution is poured out, is then added
100mL contains the aqueous solution of 10.4g phosphotungstic acid, filters after impregnating 5min, in relative degree of vacuum is -0.1MPa by obtained solid
Under, then 110 DEG C of dry 8.0h are added 100mL Mo-Co-P aqueous solution and then heat up after mixing in 70 DEG C of dry 4h
Catalyst is made, wherein MoO to 110 DEG C of dry 4h by obtained solid in 500 DEG C of roasting 3.0h3Content is 5wt%, Co2O3
Content is 1wt%, P content 0.5wt%, (NH4)0.1H2.9PW12O40Content is 10wt%.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst each point by SEM, the results showed that be distributed in catalyst external surface to 30 um of center thickness
Heteropoly acid ammonium salt content in degree is the 97wt% of total content.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 2.
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 1,2 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 1, the difference is that handling without using auxiliary agent B diesel oil catalyst precarsor A.
(1) preparation of catalyst:
Catalyst precarsor A is added to 150mL to contain in the aqueous solution of 40.2g citric acid, after impregnating 30min, solution is poured out,
Then the sal volatile that 150mL mass fraction is 30% is added and impregnates 5min, solution is poured out, 100mL is then added and contains
The aqueous solution of 10.4g phosphotungstic acid filters after impregnating 5min, by obtained solid 350 DEG C of high-temperature process 4.0h in a nitrogen atmosphere,
Obtain catalyst precarsor B；Then 100mL Mo-Co-P aqueous solution is added to then heat to after mixing in 70 DEG C of dry 4h
Then in 500 DEG C of 3.0 h of roasting catalyst is made, wherein MoO in 110 DEG C of dry 4h3Content is 5wt%, Co2O3Content is
1wt%, P content 0.5wt%, (NH4)0.1H2.9PW12O40Content is 10wt%, and the weight of silica accounts for carrying alumina body weight
3%.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst each point by SEM, the results showed that ammonium heteropoly acids are uniformly distributed on a catalyst
's.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 2.
The physico-chemical property of 1 catalyst of table
The hydrogenation cracking activity and selectivity of 2 catalyst of table
Claims (26)
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) processing is modified to alumina support using auxiliary agent A, obtains catalyst precarsor A；
(3) the catalyst precarsor A that step (2) obtains is mixed with auxiliary agent B, is separated by solid-liquid separation after mixing, by what is obtained
Solid phase is stood at -50 DEG C~0 DEG C, preferably -30~0 DEG C；
(4) aqueous solutions of organic acids is mixed with the material that step (3) obtains, is separated by solid-liquid separation after mixing；
(5) alkaline solution containing ammonium is mixed with the solid-phase material that step (4) obtains, is separated by solid-liquid separation after mixing；
(6) heteropoly acid aqueous solution is mixed with the solid-phase material that step (5) obtains, is separated by solid-liquid separation after mixing, separated
Obtained solid phase is dried to obtain catalyst precarsor B；
(7) aqueous solution that step (1) obtains is mixed with catalyst precarsor B, is urged after drying, roasting after being uniformly mixed
Agent.
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 the metal containing group VIII.
3. preparation method according to claim 2, 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 compound containing hydrogenation metal component is preferably
Molybdate compound and cobalt compound.
5. preparation method described in accordance with the claim 3, it is characterised in that: the molybdate compound is molybdenum oxide and/or seven molybdenums
Sour ammonium；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: the phosphorus-containing compound be phosphoric acid, ammonium dihydrogen phosphate,
One or more of 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: modification process described in step (2) is as follows:
(2.1) auxiliary agent A is mixed with organic solvent, obtains solution I after mixing；
(2.2) alumina support is mixed with solution I, is reacted after mixing, then through being dried to obtain catalyst precarsor
B。
9. preparation method according to claim 8, it is characterised in that: auxiliary agent A described in step (2.1) is octadecyl
Trimethoxy silane, hexadecyl trimethoxy silane, dodecyltrimethoxysilane, octadecyl trichlorosilane alkane, 16
One or more of alkyltrichlorosilanes, dodecyltrichlorosilane.
10. preparation method according to claim 8, it is characterised in that: organic solvent described in step (2.1) be benzene,
One or more of toluene, hexamethylene.
11. preparation method according to claim 8, it is characterised in that: the mass ratio of auxiliary agent A and organic solvent be 1:1~
1:50。
12. preparation method according to claim 8, it is characterised in that: reaction temperature described in step (2.2) is 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.
13. preparation method described in accordance with the claim 1, it is characterised in that: auxiliary agent B described in step (3) 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.
14. preparation method according to claim 13, it is characterised in that: the diesel oil is straight-run diesel oil, hydrogenated diesel oil, coke
Change diesel oil, one of catalytic diesel oil or a variety of, it is preferred to use hydrogenated diesel oil.
15. preparation method according to claim 13, it is characterised in that: the diesel oil uses commercial goods diesel oil, such as 5#
One of diesel oil, 0# diesel oil, -10# diesel oil, -20# diesel oil, -35# diesel oil are a variety of.
16. preparation method described in accordance with the claim 1, it is characterised in that: the auxiliary agent B and the volume ratio of aluminium oxide be 1~
4:1, preferably 1~2:1.
17. preparation method described in accordance with the claim 1, it is characterised in that: organic acid described in step (4) 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.
18. preparation method described in accordance with the claim 1, it is characterised in that: the alkaline solution containing ammonium described in step (5) is
One of ammonium hydroxide, sal volatile, ammonium bicarbonate soln are a variety of.
19. preparation method described in accordance with the claim 1, it is characterised in that: heteropoly acid described in step (6) be phosphotungstic acid,
One of silico-tungstic acid, phosphomolybdic acid are a variety of.
20. preparation method described in accordance with the claim 1, it is characterised in that: isolated solid phase is in nitrogen described in step (6)
Catalyst precarsor B is obtained after carrying out high-temperature process under gas atmosphere, the treatment temperature is 300~400 DEG C, the time is 2.0~
5.0h。
21. preparation method described in accordance with the claim 1, it is characterised in that: drying described in step (7) temperature be 60~
120 DEG C, drying time is 3.0~12.0h；The drying is carried out preferably by the way of Two stage dryer, and wherein first segment is dry
Temperature is 60~90 DEG C, and second segment drying temperature is 90~120 DEG C；The maturing temperature is 400~550 DEG C, calcining time
For 2.0~6.0h.
22. a kind of hydrocracking catalyst obtained using preparation method described in any claim in claim 1-21,
Be characterized in that: on the basis of the weight of catalyst, the content of acidic components is 10%~30%, and the content of hydrogenation metal component is 6%
~25%, auxiliary agent content is 1.0%~4.6%, and the content of carrier is 40.4%~83.0%.
23. according to the hydrocracking catalyst described in claim 22, it is characterised in that: the ratio table of the hydrocracking catalyst
Area is 140~280m20.2~0.6mL/g of/g, Kong Rongwei, average pore diameter are 5.0~10.0nm.
24. according to the hydrocracking catalyst described in claim 22, it is characterised in that: described miscellaneous in hydrocracking catalyst
Polyacid ammonium salt be distributed in content of the catalyst external surface into 30 μ m thick of center account for the 92wt% of ammonium heteropoly acids total content~
100wt%, preferably 95wt%~98wt%.
25. according to the hydrocracking catalyst described in claim 22, it is characterised in that: the catalyst acid content 85wt%~
95wt% integrated distribution is in catalyst external surface into 30 μ m thick of center.
26. according to the hydrocracking catalyst described in claim 22, it is characterised in that: the ammonium heteropoly acids 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；Work as Y
When representing P, m+n=3, n value is 0.1~1.0.
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