CN115999628A - Hydrocracking catalyst, preparation method and application thereof, and aromatic-rich cracking distillate hydrocracking method - Google Patents
Hydrocracking catalyst, preparation method and application thereof, and aromatic-rich cracking distillate hydrocracking method Download PDFInfo
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Abstract
The invention relates to a hydrocracking catalyst, a preparation method and application thereof, and an aromatic-rich cracking distillate oil hydrocracking method. The hydrocracking catalyst comprises: a) 5-20% Ni; b) 0.01 to 5 percent of CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the c) 55.00-89.99% ZSM-5; d) 5.00-20.00% of adhesive; wherein the TPR hydrogen atmosphere reduction temperature of the catalyst is lower than 420 ℃, and the dispersity of the active component Ni is higher than 8%. Through selective hydrocracking of tetrahydronaphthalene in the second-stage hydrogenation product, selective ring-opening dealkylation of polycyclic aromatic hydrocarbon and the like are carried out to generate BTX, and meanwhile, by-product C2-C5 light hydrocarbon is produced, for the final distillation point of less than 280 ℃, the total aromatic content is more than 90% of aromatic-rich distillate oil, the liquid yield of the hydrocracking product is more than 80%, and the liquid phase yield of BTX is more than 55%.
Description
Technical Field
The invention relates to a hydrocracking catalyst, a preparation method and application thereof, and an aromatic-rich cracking distillate oil hydrocracking method.
Background
The aromatic-rich pyrolysis distillate oil is a product of high-temperature condensation of raw materials and products of ethylene pyrolysis raw materials in steam pyrolysis, and mainly comes from a quenching oil tower kettle and a heavy fuel oil stripping tower kettle. The aromatic-rich pyrolysis distillate is a heavy distillate (higher than 205 ℃) rich in aromatic hydrocarbon (the aromatic hydrocarbon content is higher than 90%), the main components of the aromatic-rich pyrolysis distillate are monocyclic and polycyclic aromatic hydrocarbon compounds, the side chains are short, the hydrocarbon ratio is high, the heavy metal and ash content are low, and meanwhile, the ethylene tar also contains heterocyclic compounds of N, S, O and other elements. The yield of ethylene tar varies depending on the cracking feedstock, and generally accounts for about 1/5 of the ethylene yield, which tends to increase with the heavies of the ethylene feedstock.
The yield of each distillation section of the aromatic-rich pyrolysis distillate oil is higher and is nearly 60 percent, and the distillate oil is secondarily an extra heavy colloid asphaltene component. Meanwhile, the aromatic-rich pyrolysis distillate oil has high sulfur content, high content of polycyclic aromatic hydrocarbon and high density. The primary distillation point-205 deg.c fraction has indene and its homolog as main component, the 205-225 deg.c fraction is naphthalene, the 225-245 deg.c fraction is methyl naphthalene, the 245-300 deg.c fraction is dimethyl naphthalene, the 300-360 deg.c fraction contains great amount of anthraquinone, acenaphthene, phenanthrene, etc. and the material of >360 deg.c is colloid and asphaltene with high hydrocarbon ratio. Wherein the naphthalene and the above polycyclic aromatic hydrocarbon account for more than 60 percent.
The foreign aromatic-rich pyrolysis distillate is mainly used as a raw material for producing carbon black. And a plurality of enterprises start to utilize pyrolysis fuel oil to produce aromatic hydrocarbon solvent oil, and at present, most of ethylene tar in China is used as fuel or is only subjected to primary processing, so that the utilization rate is low, and the economic benefit is poor.
The cracking C9 fraction is also an aromatic-rich cracking distillate oil, and is mainly derived from cracking gasoline C9 fraction separated after passing through a BTX tower, wherein the aromatic hydrocarbon content is up to more than 70 percent, and the aromatic hydrocarbon content accounts for 11-22 percent of the ethylene yield. Most of the pyrolysis C9 in China is only used as cheap primary raw material and fuel oil or sold after preliminary processing.
How to use these low value added aromatic rich pyrolysis distillates is a pressing problem to the petrochemical workers. Benzene (B), toluene (T) and xylene (X) are important basic organic chemical raw materials, are widely used for producing products such as polyester, chemical fiber and the like, are closely related to national economic development and people's clothing and eating activities, and have strong demands and rapid increment in recent years. Considering the abundant aromatic hydrocarbon resources in ethylene tar and cracking C9, how to convert the aromatic cracking distillate oil such as low-added-value ethylene tar oil into BTX by a catalytic conversion technology is a huge opportunity and challenge.
In the field of hydrotreating of aromatic-rich distillate, the catalytic cracking raw material hydrotreating technology has been industrially applied from the 70 th century, and has been applied to many refineries for processing sulfur-containing or high sulfur crude oil. At present, mature catalytic cracking raw material pretreatment technology is already owned at home and abroad, and mainly comprises the following steps: VGO Union and APCU (partial conversion hydrocracking) technology, haldor, UOP Inc
Aroshift technology, VGO Hydrotreating technology, chevron, VGO Hydrodesulfurization technology, exxon, T-star technology, IFP, MAKfinding technology, mobil, AKZO, kellogg, etc. In order to further improve the product quality and conversion rate, the catalytic raw material hydrogenation pretreatment process is gradually changed from the traditional hydrodesulfurization refining (HDS) to the Mild Hydrocracking (MHC) to improve the denitrification, carbon residue and polycyclic aromatic hydrocarbon saturation capacity. />
By comprehensively analyzing the above technologies, it can be found that the technologies of hydrogenation saturation and hydrocracking are commonly adopted, so that the aromatic-rich pyrolysis distillate oil with the aromatic content of more than 90 percent has high hydrogen consumption and wastes valuable aromatic resources.
Based on the technologies of distillate Hydrodesulfurization (HDS), denitrification (HDN) and the like, optimization and innovation are carried out, and benzene (B), toluene (T) and xylene (X) are produced to the maximum extent through means of hydro-upgrading, cracking, transalkylation and the like, so that ethylene tar and cracking C9 can be fully utilized, and the added value of the ethylene tar and cracking C9 can be improved.
Disclosure of Invention
The invention aims to solve the problem of low BTX yield in the prior art, and provides a hydrocracking catalyst, a preparation method and application thereof and an aromatic-rich cracking distillate oil hydrocracking method.
The first aspect of the present invention provides a hydrocracking catalyst comprising, in weight percent:
a)5～20％Ni；
b)0.01～5％CeO 2 ；
c)55.00～89.99％ZSM-5；
d) 5-20% of binder;
wherein the TPR hydrogen atmosphere reduction temperature of the catalyst is lower than 420 ℃, and the dispersity of the active component Ni is higher than 8%.
The invention also provides an application of the catalyst in hydrocracking of the aromatic-rich pyrolysis distillate.
The third aspect of the present invention provides a method for preparing the hydrocracking catalyst, which comprises the following steps: will contain CeO 2 And ZSM-5, with an impregnation solution containing a nickel source, a chelating surfactant and an alcohol amine, a first drying, a first calcination and optionally a reduction.
In a fourth aspect, the present invention provides a method for hydrocracking an aromatic-rich cracked distillate, the method comprising: the aromatic-rich pyrolysis distillate oil with the aromatic hydrocarbon content of more than 90 percent by weight and the end point of less than 280 ℃ is used as a raw material, and is contacted with a hydrocracking catalyst for hydrocracking under the hydrogen atmosphere, wherein the hydrocracking catalyst is the hydrocracking catalyst.
According to the hydrocracking catalyst provided by the invention, the chelating surfactant, such as the alkyl ethylenediamine triacetic acid surfactant and the alcohol amine organic matters, is added in the preparation process, so that the reduction temperature of the catalyst TPR in the hydrogen atmosphere is reduced, and meanwhile, cerium oxide is added in the carrier, so that the BTX yield is improved.
The hydrocracking catalyst is used as a selective hydrocracking catalyst, selective ring-opening dealkylation and other reactions of polycyclic aromatic hydrocarbon are carried out through selective hydrocracking of tetrahydronaphthalene, BTX is generated, meanwhile, C2-C5 light hydrocarbon is a byproduct, for the final distillation point of less than 280 ℃, the total aromatic content is more than 90% of aromatic-rich distillate, the liquid yield of a hydrocracking product is more than 80%, and the liquid yield of BTX is more than 55%, so that a better technical effect is achieved.
Drawings
FIG. 1 is an XRD pattern for a hydrocracking catalyst according to example 1 of the present invention;
FIG. 2 is a temperature programmed reduction TPR map of the hydrocracking catalyst of example 1 of the present invention;
FIG. 3 is a product distribution versus on-line time plot for example 1 of the present invention;
FIG. 4 is a temperature programmed reduction TPR map of the catalyst described in comparative example 1;
FIG. 5 is a graph of comparative example 1 product distribution versus on-line time.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a hydrocracking catalyst comprising, in weight percent:
a)5～20％Ni；
b)0.01～5％CeO 2 ；
c)55.00～89.99％ZSM-5；
d) 5-20% of binder;
wherein the TPR hydrogen atmosphere reduction temperature of the catalyst is lower than 420 ℃, and the dispersity of the active component Ni is higher than 8%.
In the invention, the dispersity test method of the active component Ni is an oxyhydrogen titration method.
Wherein: dispersity of R- - - -Ni;
[ Ni ] - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -;
[Ni] total (S) -total nickel atom number;
V 0 -titration amount of hydrogen, mL;
N A -Avgalileo constant (6.023). Times.10 23 ；
W- -pattern mass, g;
p- -the mass fraction of nickel in the form,%;
m- -atomic weight of nickel 58.7.
In the invention, the test method of TPR hydrogen atmosphere reduction is an oxyhydrogen titration method.
The hydrocracking catalyst is particularly suitable for being used as a selective hydrocracking catalyst, can be used for selectively hydrocracking tetralin compounds, selectively ring-opening dealkylating polycyclic aromatic hydrocarbons and the like to generate BTX, and simultaneously produces byproducts C2-C5 light hydrocarbons, and has good hydrocracking effect on aromatic-rich distillate oil with the final distillation point of less than 280 ℃ and the total aromatic content of more than 90 weight percent, wherein the liquid phase yield of the BTX is more than 55 percent.
According to a preferred embodiment of the present invention, the catalyst has a TPR hydrogen atmosphere reduction peak temperature of less than 400 ℃, preferably a TPR hydrogen atmosphere reduction peak temperature of less than 390 ℃; the dispersity of the active component Ni in the catalyst is more than 8%, and preferably the dispersity of the active component Ni is more than 10%.
According to a preferred embodiment of the present invention, the catalyst has Ni content of 10-15% by weight and CeO content 2 The content is 0.5-3%, the binder content is8-15% and ZSM-5 as the rest.
In the invention, for the hydrogenation of the easily coked component, adding an anti-coking agent into the hydrocracking catalyst is a routine choice in the field, and for the invention, alkaline earth metals such as calcium and the like can be added into the hydrocracking catalyst as the anti-coking agent. According to a preferred embodiment of the invention, the catalyst preferably contains from 0.1 to 3.0wt% of alkaline earth metal oxide, preferably the alkaline earth metal oxide is calcium oxide and/or magnesium oxide.
In the present invention, there is no particular requirement for the binder, and conventional binders in the art are suitable for the present invention, and for the present invention, the binder is selected from alumina and/or silica, preferably, the binder source is selected from at least one of silica sol, water glass, pseudo-boehmite, white carbon black and alumina sol.
The catalyst having the aforementioned properties of the present invention can be used in the present invention, and there is no particular requirement for the preparation method thereof, and according to a preferred embodiment of the present invention, there is provided a preparation method of the hydrocracking catalyst, comprising: will contain CeO 2 And ZSM-5, and contacting the composite carrier with an impregnating solution containing a nickel source, a chelating surfactant and an alcohol amine for aging impregnation, first drying, first roasting and reduction. According to the method, the chelating surfactant, such as the alkyl ethylenediamine triacetic acid surfactant and the alcohol amine organic matters, is added in the preparation process of the hydrocracking catalyst, so that the reduction temperature of the catalyst TPR in the hydrogen atmosphere is reduced, and meanwhile, cerium oxide is added in the carrier, so that the BTX yield is improved.
In the invention, for the hydrogenation of the easily coked component, adding an anti-coking agent into the hydrocracking catalyst is a routine choice in the field, and for the invention, alkaline earth metals such as calcium and the like can be added into the hydrocracking catalyst as the anti-coking agent. According to a preferred embodiment of the present invention, the catalyst contains CeO 2 And ZSM-5 composite carrier contains alkaline earth metal oxide, and the specific dosage is selected according to the requirement.
In the present invention, the nickel source may be selected from a wide range, and according to a preferred embodiment of the present invention, the nickel source is selected from at least one of nickel nitrate, nickel acetate and basic nickel carbonate.
In the present invention, the alcohol amine is selected from a wide range, and according to a preferred embodiment of the present invention, the alcohol amine is one or more of triethanolamine, diethanolamine, and ethanolamine. This can improve the hydrocracking selective hydrogenation effect.
In the invention, the chelating surfactant has wide optional range, and according to a preferred embodiment of the invention, the chelating surfactant is an alkyl ethylenediamine triacetic surfactant; preferably, the alkyl ethylenediamine triacetic acid surfactant is selected from one or more of sodium N-dodecyl ethylenediamine triacetate, sodium N-hexadecyl ethylenediamine triacetate and sodium N-octadecyl ethylenediamine triacetate. This can improve the hydrocracking selective hydrogenation effect.
According to a preferred embodiment of the present invention, the chelating surfactant is used in an amount of 0.01 to 5% and the alcohol amine is used in an amount of 0.01 to 5% based on the total weight of the impregnating solution. This can improve the hydrocracking selective hydrogenation effect.
In the present invention, there is no particular requirement on the impregnation method, and conventional impregnation methods and conditions may be employed, and according to a preferred embodiment of the present invention, the impregnation conditions include: the isovolumetric impregnation may be, for example, spray impregnation.
According to a preferred embodiment of the invention, the conditions of impregnation comprise: the aging temperature is 10 to 80℃and preferably 15 to 20 ℃.
According to a preferred embodiment of the invention, the ageing time is between 0.5 and 24 hours.
The invention is not particularly limited to the drying conditions, and common drying conditions may be used in the invention, and according to a preferred embodiment of the invention, the first drying conditions include: the temperature is 30-200 ℃.
The present invention has no special requirements on the conditions of firing, and common conditions of firing can be used in the present invention, and according to a preferred embodiment of the present invention, the conditions of the first firing include: the temperature is 300-600 ℃, and the time is as follows: and 0.5 to 24 hours.
According to a preferred embodiment of the invention, the catalyst is prepared by adopting an isovolumetric impregnation method, the impregnation temperature is 10-80 ℃, the catalyst is impregnated on the composite carrier by adopting a spraying method, the catalyst is placed for 0.5-24 hours after the impregnation, and the catalyst is dried at 30-200 ℃ and then baked for 0.5-24 hours at 300-600 ℃ to obtain the finished catalyst.
According to a preferred embodiment of the present invention, the catalyst contains CeO 2 The preparation method of the ZSM-5 composite carrier comprises the following steps: mixing ZSM-5 powder, optional alkaline earth metal source, cerium source, binder source, optional auxiliary agent source and acid liquor, kneading, molding, secondary drying and secondary roasting; this can improve the hydrocracking selective hydrogenation effect.
According to a preferred embodiment of the present invention, preferably, the catalyst contains CeO 2 The preparation method of the ZSM-5 composite carrier comprises the following steps: mixing an adhesive source, ZSM-5 powder and optional auxiliary agent to obtain a first mixture, and then mixing and contacting the first mixture with an acid solution containing a cerium source and optional alkaline earth metal source for kneading, forming, drying for the second time and roasting for the second time; preferably, the weight ratio of the first mixture to the acid liquor is 100:5-100:100. This can improve the hydrocracking selective hydrogenation effect.
According to a preferred embodiment of the present invention, the ZSM-5 powder is in the hydrogen form, siO 2 /Al 2 O 3 The molar ratio is 50 to 500, preferably 50 to 300, more preferably 100 to 250.
The invention has no special requirements on the type of the binder source, and common binder sources can be used in the invention, and according to a preferred embodiment of the invention, the binder source is selected from at least one of silica sol, water glass, pseudo-boehmite, white carbon black and alumina sol, preferably at least one of pseudo-boehmite, water glass and silica sol.
The invention has no special requirements on the types of auxiliary sources, and common auxiliary sources can be used in the invention, and according to a preferred embodiment of the invention, the auxiliary sources are at least one selected from methylcellulose, sesbania powder, polyethylene glycol, calcium nitrate, magnesium nitrate and hydroxymethyl cellulose.
The present invention has no special requirement on the kind of acid source, and common acid sources can be used in the present invention, and according to a preferred embodiment of the present invention, the acid substance of the acid solution is at least one selected from nitric acid, phosphoric acid, acetic acid, citric acid and tartaric acid.
According to a preferred embodiment of the invention, the acid solution is an acidic aqueous solution having a concentration of 1 to 6% by weight. This can improve the hydrocracking selective hydrogenation effect.
In the present invention, the alkaline earth metal source is not particularly limited, and may be, for example, a commonly used alkaline earth metal compound, for example, calcium nitrate when the alkaline earth metal is calcium, which is merely an exemplary illustration, and thus does not limit the scope of the present invention.
The conditions of the second firing are not particularly limited in the present invention, and according to a preferred embodiment of the present invention, the conditions of the second firing include: roasting for 0.5-24 h at 450-750 ℃, preferably for 1-24h at 480-650 ℃.
The invention provides an application of the catalyst in hydrocracking of aromatic-rich pyrolysis distillate oil. The catalyst is particularly suitable for hydrocracking of aromatic-rich pyrolysis distillate oil, and has good selective hydrogenation effect.
The invention provides a hydrocracking method of aromatic-rich pyrolysis distillate, which comprises the following steps: the aromatic-rich pyrolysis distillate oil with the aromatic hydrocarbon content of more than 90 percent by weight and the end point of less than 280 ℃ is used as a raw material, and is contacted with a hydrocracking catalyst for hydrocracking under the hydrogen atmosphere, wherein the hydrocracking catalyst is the hydrocracking catalyst. The aromatic-rich cracked distillate oil of the invention has good selective hydrogenation effect.
In the present invention, the optional range of hydrocracking conditions is broad, and according to a preferred embodiment of the present invention, the hydrocracking conditions include: the pressure is 2-8 Mpa.
In the present invention, the optional range of hydrocracking conditions is broad, and according to a preferred embodiment of the present invention, the hydrocracking conditions include: space velocity of 0.8-6h -1 。
In the present invention, the optional range of hydrocracking conditions is broad, and according to a preferred embodiment of the present invention, the hydrocracking conditions include: the temperature is 260-500 ℃.
According to a preferred embodiment of the invention, aromatic-rich distillate oil with the aromatic hydrocarbon content of more than 90 percent and the final distillation point of less than 280 ℃ is taken as a raw material, and is contacted with a hydrocracking catalyst for hydrocracking under the hydrogen atmosphere; the hydrocracking conditions include: the pressure is 2-8 Mpa; space velocity of 0.8-6h -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature is 260-500 ℃. The hydrocracking catalyst provided by the invention has a good hydrocracking effect on the hydrocracking of the aromatic-rich distillate oil with the final distillation point less than 280 ℃ and the total aromatic content more than 90 wt%, wherein the BTX liquid phase yield can be more than 55%.
For the convenience of understanding the present invention, examples are set forth below, but are merely to aid in understanding the present invention and are not to be construed as limiting the invention in any way.
In the following examples, the method for evaluating hydrocracking of aromatic-rich cracked distillate oil comprises:
aromatic-rich cracking raw materials: the distillation range is 165-258 ℃, the sulfur content is=0.5 ppm, and the nitrogen content is=0.2 ppm; the raw materials comprise: 5.08wt% of non-aromatic; 35.96wt% of alkylbenzene; indanes 22.05 wt.%; 32.37wt% of tetrahydronaphthalene; 2.50wt% of naphthalene; benzene 0.204wt%.
Evaluation conditions: inlet temperature t=400 ℃; volume space velocity v=1.2; h 2 Oil (v/v) =600; pressure = 4.0MPa.
Liquid phase product yield = W Liquid product /W Raw materials
W Liquid product -weight of liquid phase reaction product in line 24 hours, grams;
W raw materials -in-line 24 hours of cracking of the feed of distillate, grams.
The dispersity test method of the active component Ni is an oxyhydrogen titration method, and the test method is as follows:
wherein: dispersity of R- - - -Ni;
[ Ni ] - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -;
[Ni] total (S) -total nickel atom number;
V 0 -titration amount of hydrogen, mL;
N A -Avgalileo constant (6.023). Times.10 23 ；
W- -pattern mass, g;
p- -the mass fraction of nickel in the form,%;
m- -atomic weight of nickel 58.7.
Liquid phase product yield calculation method
Liquid phase product yield = W Liquid product /W Raw materials
W Liquid product -weight of liquid phase reaction product in line 24 hours, grams;
W raw materials -in-line 24 hours of cracking of the feed of distillate, grams.
Active ingredient Ni reduction peak temperature determination
Adopts a TPR programmed heating reduction method, adopts hydrogen atmosphere for reduction, and has the heating rate of 10 ℃/min and the heating rate of 900 ℃.
Example 1
Hydrogen type SiO 2 /Al 2 O 3 850 g of ZSM-5 molecular sieve powder with the molar ratio of 150, 15 g of pseudo-boehmite, 15 g of methylcellulose and 15 g of sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 8 g of cerium oxide and calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing at 20 ℃ for 12 hours, drying at 110 ℃ for 6 hours, and placing into a muffle furnace for roasting at 600 ℃ for 5 hours to obtain the composite carrier, wherein the water absorption rate is 102%. The composition of the raw materials for preparing the composite carrier, the reaction conditions and the water absorption of the composite carrier are shown in table 1 and table 2.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 1 g of N-dodecyl ethylenediamine sodium triacetate and 1 g of triethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a rotary pot spraying method, ageing for 16 hours, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃, and obtaining the oxidation catalyst, and reducing for 48 hours in a hydrogen atmosphere at 350 ℃ to obtain the hydrocracking catalyst. The composition of the raw materials for preparing the composite carrier, the reaction conditions and the water absorption rate of the composite carrier are shown in tables 1 and 2. The XRD patterns of the hydrogen type ZSM-5 powder, the composite carrier and the catalyst are shown in figure 1, and the fact that the ZSM-5 structure is not affected in the carrier forming and catalyst active component loading process can be seen from figure 1; the dispersity of the reduced catalyst Ni is shown in Table 5; the temperature programmed reduction TPR map of the oxidative catalyst is shown in figure 2, and the peak value of the reduction temperature of the active component in the hydrogen atmosphere is 376 ℃ as can be seen from figure 2, which shows that the active component is well dispersed, easy to reduce and high in activity.
The TPR temperature programmed reduction peak temperatures of the oxidative catalysts are shown in table 6. The conditions for the catalyst preparation are shown in tables 3 and 4.
The evaluation results are shown in Table 5 and FIG. 3, and it can be seen from FIG. 3 that the catalyst reactivity remained substantially unchanged in 500 hours on line.
Example 2
Selecting hydrogen type SiO 2 /Al 2 O 3 100 of ZSM-5 molecular sieve powder 850 g, pseudo-boehmite 150 g, methylcellulose and sesbania powder 15 g are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 40 g of cerium oxide and calcium nitrate containing 20 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing at 15 ℃ for 20 hours, drying at 100 ℃ for 8 hours, placing into a muffle furnace, and roasting at 600 ℃ for 5 hours to obtain the composite carrier, wherein the water absorption is 101%, and the composition and reaction conditions of the composite carrier preparation raw materials and the water absorption of the composite carrier are shown in tables 1 and 2.
Preparing an impregnating solution containing 35 g of Ni by using a soluble metal salt precursor nickel nitrate, controlling the volume of the solution to 165 ml, adding 1 g of N-hexadecyl ethylenediamine sodium triacetate and 1 g of diethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 165 g of composite carrier, loading the impregnating solution on the composite carrier in equal volume by adopting a rotary pot spraying method, ageing for 20 hours at 15 ℃, drying for 4 hours at 110 ℃, roasting for 4 hours at 380 ℃, obtaining an oxidation catalyst, and reducing for 48 hours in a hydrogen atmosphere at 400 ℃, wherein the dispersity of the Ni of the reduction catalyst is shown in Table 5. The conditions for the catalyst preparation are shown in tables 3 and 4. The TPR temperature programmed reduction peak temperature of the oxidative catalyst is shown in Table 5.
The evaluation results are shown in Table 5.
Example 3
Selecting hydrogen type SiO 2 /Al 2 O 3 850 g of ZSM-5 molecular sieve powder of 250, 150 g of pseudo-boehmite, 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 13 g of nitric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 20 g of cerium oxide and calcium nitrate containing 15 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing at 20 ℃ for 12 hours, drying at 110 ℃ for 6 hours, placing into a muffle furnace, and roasting at 550 ℃ for 6 hours to obtain the composite carrier, wherein the water absorption is 105%, and the composition and the reaction conditions of the preparation raw materials of the composite carrier and the water absorption of the composite carrier are shown in tables 1 and 2.
Preparing an impregnating solution containing 40 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 160 ml, adding 1 g of N-dodecyl ethylenediamine sodium triacetate, 0.8 g of ethanolamine and 0.8 g of triethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 160 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume by adopting a rotary pot spraying method, ageing for 16 hours at 20 ℃, drying for 3 hours at 180 ℃, roasting for 2 hours at 600 ℃, obtaining an oxidation catalyst, and reducing for 40 hours in a hydrogen atmosphere at 450 ℃, wherein the dispersity of the Ni of the reduction catalyst is shown in Table 5. The conditions for the catalyst preparation are shown in tables 3 and 4. The TPR temperature programmed reduction peak temperature of the oxidative catalyst is shown in Table 5.
The evaluation results are shown in Table 5.
Example 4
Selecting hydrogen type SiO 2 /Al 2 O 3 850 g of ZSM-5 molecular sieve powder of 200, 150 g of pseudo-boehmite and Tianfen g of uniformly mixed for standby; adding 12 g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 20 g of cerium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing at 20 ℃ for 12 hours, drying at 110 ℃ for 6 hours, and placing into a muffle furnace to bake at 480 ℃ for 24 hours to obtain the composite carrier, wherein the water absorption is 102%, and the composition and reaction conditions of the preparation raw materials of the composite carrier and the water absorption of the composite carrier are shown in tables 1 and 2.
Preparing an impregnating solution containing 20 g of Ni by using a soluble metal salt precursor nickel acetate, controlling the volume of the solution to 170 ml, adding 1 g of N-hexadecyl ethylenediamine sodium triacetate and 2 g of diethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the same volume of the impregnating solution on the composite carrier by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 2 hours at 180 ℃, roasting for 3 hours at 500 ℃, obtaining an oxidation catalyst, and reducing for 40 hours in a hydrogen atmosphere at 400 ℃, wherein the dispersity of the Ni of the reduction catalyst is shown in Table 5. The conditions for the catalyst preparation are shown in tables 3 and 4. The TPR temperature programmed reduction peak temperature of the oxidative catalyst is shown in Table 5.
The evaluation results are shown in Table 5.
Example 5
Selecting hydrogen type SiO 2 /Al 2 O 3 900 g of ZSM-5 molecular sieve powder of 200, 100 g of pseudo-boehmite and 30 g of methylcellulose are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 550 g of water to dissolve uniformly, adding cerium nitrate containing 30 g of cerium oxide and calcium nitrate containing 8 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing at 20 ℃ for 24 hours, drying at 100 ℃ for 8 hours, placing into a muffle furnace, and roasting at 650 ℃ for 1 hour to obtain the composite carrier, wherein the water absorption rate is 110%, and the composition and reaction conditions of the composite carrier preparation raw materials and the water absorption rate of the composite carrier are shown in tables 1 and 2.
Preparing an impregnating solution containing 25 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 175 ml, adding 1 g of N-dodecyl ethylenediamine sodium triacetate, 0.4 g of ethanolamine, 0.4 g of diethanolamine and 0.2 g of triethanolamine into the impregnating solution, uniformly stirring and dissolving, taking 175 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 10 hours at 100 ℃, roasting for 3 hours at 450 ℃, obtaining an oxidation catalyst, reducing for 52 hours in a hydrogen atmosphere at 350 ℃, and obtaining a reduction catalyst, wherein the dispersity of Ni of the reduction catalyst is shown in Table 5. The conditions for the catalyst preparation are shown in tables 3 and 4. The TPR temperature programmed reduction peak temperature of the oxidative catalyst is shown in Table 5.
The evaluation results are shown in Table 5.
Example 6
Selecting hydrogen type SiO 2 /Al 2 O 3 900 g of ZSM-5 molecular sieve powder of 200, 100 g of water glass and 15 g of methylcellulose and sesbania powder respectively are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 15 g of cerium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing at 20 ℃ for 12 hours, drying at 120 ℃ for 5 hours, and placing into a muffle furnace for roasting at 500 ℃ for 10 hours to obtain the composite carrier, wherein the water absorption rate is 108%, and the composition and the reaction conditions of the preparation raw materials of the composite carrier and the water absorption rate of the composite carrier are shown in tables 1 and 2.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 2 g of N-hexadecyl ethylenediamine sodium triacetate and 2 g of ethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the same volume of the impregnating solution on the composite carrier by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 6 hours at 400 ℃, obtaining an oxidation catalyst, and reducing for 42 hours in a hydrogen atmosphere at 400 ℃, wherein the dispersity of Ni of the reduction catalyst is shown in Table 5. The conditions for the catalyst preparation are shown in tables 3 and 4. The TPR temperature programmed reduction peak temperature of the oxidative catalyst is shown in Table 5.
The evaluation results are shown in Table 5.
Example 7
Selecting hydrogen type SiO 2 /Al 2 O 3 800 g of ZSM-5 molecular sieve powder of 150, 200 g of pseudo-boehmite, 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 550 g of water to dissolve uniformly, adding cerium nitrate containing 15 g of cerium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing at 20 ℃ for 12 hours, drying at 110 ℃ for 6 hours, and placing into a muffle furnace for roasting at 600 ℃ for 4 hours to obtain the composite carrier, wherein the water absorption is 103%, and the composition and the reaction conditions of the preparation raw materials of the composite carrier and the water absorption of the composite carrier are shown in tables 1 and 2.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 4 g of N-octadecyl ethylenediamine sodium triacetate and 0.5 g of diethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃ to obtain an oxidation catalyst, and reducing for 42 hours in a hydrogen atmosphere at 400 ℃ to obtain a reduction catalyst, wherein the dispersity of Ni of the reduction catalyst is shown in Table 5. The conditions for the catalyst preparation are shown in tables 3 and 4. The TPR temperature programmed reduction peak temperature of the oxidative catalyst is shown in Table 5.
The evaluation results are shown in Table 5.
Example 8
Selecting hydrogen type SiO 2 /Al 2 O 3 900 g of ZSM-5 molecular sieve powder of 150, 100 g of silica sol, 15 g of methylcellulose and sesbania powder respectively are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 550 g of water to dissolve uniformly, adding cerium nitrate containing 5 g of cerium oxide and calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the above mixed powder, kneading for 35 min, extruding to form strips, placing at 20 ℃ for 12 hours, drying at 110 ℃ for 6 hours, placing into a muffle furnace, roasting at 600 ℃ for 4 hours to obtain the composite carrier, wherein the water absorption rate is 103%, and the composite carrier is prepared from raw material components and reaction stripsThe water absorption of the parts and the composite carrier are shown in tables 1 and 2.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 0.02 g of N-hexadecyl ethylenediamine sodium triacetate and 8 g of ethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃, obtaining an oxidation catalyst, and reducing for 42 hours in a hydrogen atmosphere at 400 ℃, wherein the dispersity of Ni of the reduction catalyst is shown in Table 5. The conditions for the catalyst preparation are shown in tables 3 and 4. The TPR temperature programmed reduction peak temperature of the oxidative catalyst is shown in Table 5.
The evaluation results are shown in Table 5.
Example 9
Selecting hydrogen type SiO 2 /Al 2 O 3 900 g of ZSM-5 molecular sieve powder of 150, 100 g of pseudo-boehmite, 20 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 550 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing at 20 ℃ for 12 hours, drying at 110 ℃ for 6 hours, placing into a muffle furnace, and roasting at 600 ℃ for 4 hours to obtain the composite carrier, wherein the water absorption is 101%, and the composition and reaction conditions of the composite carrier preparation raw materials and the water absorption of the composite carrier are shown in tables 1 and 2.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 8 g of N-dodecyl ethylenediamine sodium triacetate and 0.02 g of diethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the same volume of the impregnating solution on the composite carrier by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃, obtaining an oxidation catalyst, and reducing for 42 hours in a hydrogen atmosphere at 400 ℃, wherein the dispersity of Ni of the reduction catalyst is shown in Table 5. The conditions for the catalyst preparation are shown in tables 3 and 4. The TPR temperature programmed reduction peak temperature of the oxidative catalyst is shown in Table 5.
The evaluation results are shown in Table 5.
Example 10
Hydrogen type SiO 2 /Al 2 O 3 850 g of ZSM-5 molecular sieve powder with the molar ratio of 150, 15 g of pseudo-boehmite, 15 g of methylcellulose and 15 g of sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 8 g of cerium oxide and calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing at 20 ℃ for 12 hours, drying at 110 ℃ for 6 hours, and placing into a muffle furnace for roasting at 600 ℃ for 5 hours to obtain the composite carrier, wherein the water absorption rate is 102%. The composition of the raw materials for preparing the composite carrier, the reaction conditions and the water absorption of the composite carrier are shown in table 1 and table 2.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 0.0085 g of N-dodecyl ethylenediamine sodium triacetate and 0.0085 g of triethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume by adopting a rotary pot spraying method, ageing for 16 hours, drying at 100 ℃ for 4 hours, roasting at 400 ℃ for 4 hours to obtain an oxidation catalyst, and reducing at 350 ℃ in hydrogen atmosphere for 48 hours to obtain the hydrocracking catalyst. The composition of the raw materials for preparing the composite carrier, the reaction conditions and the water absorption rate of the composite carrier are shown in tables 1 and 2. The dispersity of the reduced catalyst Ni is shown in Table 5.
The TPR temperature programmed reduction peak temperatures of the oxidative catalysts are shown in table 6. The conditions for the catalyst preparation are shown in tables 3 and 4.
The evaluation results are shown in Table 5.
Example 11
Hydrogen type SiO 2 /Al 2 O 3 850 g of ZSM-5 molecular sieve powder with the molar ratio of 500, 15 g of pseudo-boehmite, 15 g of methylcellulose and 15 g of sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to be dissolved uniformly, and adding the water containing 8 g of nitric acidCerium nitrate calculated by gram cerium oxide and calcium nitrate containing 10 gram calcium oxide are dissolved uniformly, the solution is poured into the mixed powder for kneading for 35 minutes, extruded and molded, and after being placed at 20 ℃ for 12 hours, dried at 110 ℃ for 6 hours, and then placed in a muffle furnace for roasting at 600 ℃ for 5 hours, thus obtaining the composite carrier, and the water absorption rate of the composite carrier is 102%. The composition of the raw materials for preparing the composite carrier, the reaction conditions and the water absorption of the composite carrier are shown in table 1 and table 2.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 1 g of N-dodecyl ethylenediamine sodium triacetate and 1 g of triethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a rotary pot spraying method, ageing for 16 hours, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃, and obtaining the oxidation catalyst, and reducing for 48 hours in a hydrogen atmosphere at 350 ℃ to obtain the hydrocracking catalyst. The composition of the raw materials for preparing the composite carrier, the reaction conditions and the water absorption rate of the composite carrier are shown in tables 1 and 2. The dispersity of the reduced catalyst Ni is shown in Table 5.
The TPR temperature programmed reduction peak temperatures of the oxidative catalysts are shown in table 6. The conditions for the catalyst preparation are shown in tables 3 and 4.
The evaluation results are shown in Table 5.
Example 12
Hydrogen type SiO 2 /Al 2 O 3 850 g of ZSM-5 molecular sieve powder with the molar ratio of 150, 15 g of pseudo-boehmite, 15 g of methylcellulose and 15 g of sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing for 12 hours at 20 ℃, drying for 6 hours at 110 ℃, and placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 102%. The composition of the raw materials for preparing the composite carrier, the reaction conditions and the water absorption of the composite carrier are shown in table 1 and table 2.
Preparing an impregnating solution containing 12 g of Ni and cerium nitrate calculated by 8 g of cerium oxide by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 188 ml, adding 1 g of N-dodecyl ethylenediamine sodium triacetate and 1 g of triethanolamine into the impregnating solution, uniformly stirring and dissolving, taking 188 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a rotary pot spraying method, ageing for 16 hours, drying at 100 ℃ for 4 hours, roasting at 400 ℃ for 4 hours to obtain an oxidation catalyst, and reducing at 350 ℃ in a hydrogen atmosphere for 48 hours to obtain the hydrocracking catalyst. The dispersity of the reduced catalyst Ni is shown in Table 5. The TPR temperature programmed reduction peak temperatures of the oxidative catalysts are shown in table 6. The conditions for the catalyst preparation are shown in tables 3 and 4.
Comparative example 1
Selecting hydrogen type SiO 2 /Al 2 O 3 850 g of ZSM-5 molecular sieve powder of 150, 15 g of pseudo-boehmite, 15 g of methylcellulose and 15 g of sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 8 g of cerium oxide and calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours to obtain the composite carrier, wherein the water absorption rate is 102%.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, taking 170 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume by adopting a rotary pot spraying method, ageing for 16 hours, drying for 4 hours at 100 ℃, roasting at 400 ℃ to obtain an oxidation catalyst, and reducing for 48 hours in a hydrogen atmosphere at 350 ℃ to obtain the reduction catalyst. The preparation conditions of the composite carrier and the catalyst are shown in tables 1 and 2, the temperature programmed reduction TPR map of the oxidative catalyst is shown in figure 4, and the peak reduction temperature of the active component in the hydrogen atmosphere is 442 ℃ as can be seen in figure 4, which indicates that the dispersion of the active component is poor, the reduction is difficult and the activity is low.
The evaluation results are shown in Table 5 and FIG. 5, and it can be seen from FIG. 5 that the catalyst had poor reaction stability and fast deactivation in 500 hours on line.
Comparative example 2
Selecting hydrogen type SiO 2 /Al 2 O 3 Is 150, 850 g of ZSM-5 molecular sieve powder, 15 g of pseudo-boehmite, 15 g of methylcellulose and 15 g of sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding to form strips, placing for 12 hours at 20 ℃, drying for 6 hours at 110 ℃, and placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 102%.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 1 g of N-dodecyl ethylenediamine sodium triacetate and 1 g of triethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the same volume of the impregnating solution on the composite carrier by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃, obtaining an oxidation catalyst, and reducing for 48 hours in a hydrogen atmosphere at 350 ℃, wherein the dispersity of Ni of the reduction catalyst is shown in Table 5. The preparation conditions of the composite carrier and the catalyst are shown in tables 1 and 2.
The evaluation results are shown in Table 5.
If the data in the tables are different from the embodiments, the embodiments are the same.
Because the initial reaction activity of the catalyst is not greatly different, the difference of the reaction performance of different catalysts can be obvious only after the reaction is carried out for 100 hours, such as benzene, toluene and xylene yield of target products, and the influence on the liquid yield of the products is not great. The present invention is therefore described with respect to the liquid phase yield at 400h as the catalytic effect. In the present invention, liquid recovery wt% (product data is on-line 400 hours data) refers to liquid phase yield at 400 hours on-line.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
* The product data are liquid phase yield data for 400 hours on line; * Heating rate of 10 ℃/min under hydrogen atmosphere.
As can be seen from Table 5, compared with the traditional method, the catalyst prepared by adopting the preparation method of the composite carrier and the novel impregnating solution has the advantages that the temperature programmed reduction peak temperature of the TPR of the active component nickel is obviously reduced, the dispersity is obviously improved, and the reactivity and the stability of the catalyst are obviously improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A hydrocracking catalyst characterized in that it comprises, in weight percent:
a)5～20％Ni；
b)0.01～5％CeO 2 ；
c)55.00～89.99％ZSM-5；
d) 5-20% of binder;
wherein the TPR hydrogen atmosphere reduction temperature of the catalyst is lower than 420 ℃, and the dispersity of the active component Ni is higher than 8%.
2. The catalyst according to claim 1, wherein,
in the catalyst, the Ni content is 10-15% by weight, and the CeO content is calculated by weight percent 2 The content is 0.5-3%, the binder content is 8-15%, and the balance is ZSM-5; and/or
Preferably the catalyst contains from 0.1 to 3wt% of an alkaline earth metal oxide, preferably the alkaline earth metal oxide is calcium oxide and/or magnesium oxide; and/or
The TPR hydrogen atmosphere reduction temperature of the catalyst is lower than 400 ℃, more preferably the TPR hydrogen atmosphere reduction temperature of the catalyst is lower than 390 ℃; preferably, the dispersity of the active component Ni is more than 10%.
3. Use of the catalyst of claim 1 or 2 in hydrocracking of aromatic-rich cracked distillates.
4. A process for the preparation of a catalyst according to claim 1 or 2, characterized in that it comprises: will contain CeO 2 And ZSM-5, with an impregnation solution containing a nickel source, a chelating surfactant and an alcohol amine, a first drying, a first calcination and optionally a reduction.
5. The process according to claim 4, wherein,
the CeO contains 2 And ZSM-5, the composite carrier contains alkaline earth metal oxide; and/or
The alcohol amine is one or more of triethanolamine, diethanolamine and ethanolamine; and/or
The chelating surfactant is an alkyl ethylenediamine triacetic acid surfactant;
preferably, the alkyl ethylenediamine triacetic acid surfactant is selected from one or more of N-dodecyl ethylenediamine triacetic acid sodium salt, N-hexadecyl ethylenediamine triacetic acid sodium salt and N-octadecyl ethylenediamine triacetic acid sodium salt; and/or
The total weight of the impregnating solution is 0.01-5% of chelating surfactant and 0.01-5% of alcohol amine.
6. The process according to claim 4 or 5, wherein,
the conditions of impregnation include: soaking in an equal volume; and/or the aging temperature is 10-80 ℃, preferably 15-20 ℃, and/or the aging time is 0.5-24 hours; and/or spray impregnation; and/or
The conditions of the first drying include: the temperature is 30-200 ℃; and/or
The conditions for the first firing include: the temperature is 300-600 ℃, and the time is as follows: and 0.5 to 24 hours.
7. The production method according to any one of claims 4 to 6, wherein the CeO-containing substance 2 The preparation method of the ZSM-5 composite carrier comprises the following steps:
mixing ZSM-5 powder, optional alkaline earth metal source, cerium source, binder source, optional auxiliary agent source and acid liquor, kneading, molding, secondary drying and secondary roasting;
preferably, the catalyst contains CeO 2 The preparation method of the ZSM-5 composite carrier comprises the following steps: mixing an adhesive source, ZSM-5 powder and optional auxiliary agent to obtain a first mixture, and then mixing and contacting the first mixture with an acid solution containing a cerium source and optional alkaline earth metal source for kneading, forming, drying for the second time and roasting for the second time; preferably, the weight ratio of the first mixture to the acid liquor is 100:5-100:100.
8. The preparation method according to claim 7, wherein,
the ZSM-5 powder is hydrogen type, siO 2 /Al 2 O 3 The molar ratio is 50-500, preferably 50-300, more preferably 100-250; and/or
The adhesive source is selected from at least one of silica sol, water glass, pseudo-boehmite, white carbon black and alumina sol, preferably at least one of pseudo-boehmite, water glass and silica sol; and/or
The auxiliary agent source is at least one selected from methylcellulose, sesbania powder, polyethylene glycol, calcium nitrate, magnesium nitrate and hydroxymethyl cellulose; and/or
The acid substance of the acid liquor is at least one of nitric acid, phosphoric acid, acetic acid, citric acid and tartaric acid; and/or
The acid liquor is an acidic aqueous solution with the concentration of 1-6 weight percent; and/or
The conditions for the second firing include: roasting for 0.5-24 h at 450-750 ℃, preferably for 1-24h at 480-650 ℃.
9. A process for hydrocracking an aromatic-rich cracked distillate, the process comprising: an aromatic-rich cracked distillate oil with the aromatic hydrocarbon content of more than 90 percent by weight and the end point of less than 280 ℃ is used as a raw material, and is contacted with a hydrocracking catalyst for hydrocracking under the hydrogen atmosphere, wherein the hydrocracking catalyst is the hydrocracking catalyst of claim 1 or 2.
10. The method of claim 9, wherein the hydrocracking conditions comprise:
the pressure is 2-8 Mpa; and/or space velocity of 0.8-6h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or a temperature of 260 to 500 ℃.
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