Heavy distillate oil selective hydrogenation dearomatization catalyst and preparation method and application thereof

Abstract

The present invention provides a heavy distillate oil selective hydrogenation dearomatization catalyst and a preparation method and application thereof, and relates to the technical field of catalysts, the preparation method comprises the following steps: (a) impregnating a high polymer with a catalyst carrier, and diffusing the high polymer into the pores of the catalyst carrier to obtain the catalyst carrier treated by the high polymer; wherein the high polymer accounts for 1 / 4 to 1 / 2 of the pore channel of the catalyst carrier; and (b) dipping the catalyst carrier treated by the high polymer in a metal salt solution, and then drying and roasting to obtain the catalyst for selective hydrogenation and dearomatization of heavy distillate oil. According to the invention, the technical problem of low aromatic hydrocarbon hydrogenation selectivity caused by secondary hydrogenation of aromatic hydrocarbon diffused in a catalyst pore channel is solved, and the technical effect of effectively improving the aromatic hydrocarbon hydrogenation selectivity is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and particularly to a selective hydrodearomatization catalyst for heavy distillate oil, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, the selective hydrogenation catalysts used for producing environmentally friendly rubber oil in China are mainly general distillate oil hydrofining catalysts or hydrotreating catalysts. The design purpose of these catalysts is mainly to remove sulfur, nitrogen, and aromatic hydrocarbon content in oil as much as possible, but the performance of selective hydrogenation of aromatic hydrocarbons (the ability to remove polycyclic aromatic hydrocarbons as much as possible while retaining monocyclic and bicyclic aromatic hydrocarbons) is still not ideal.

[0003] The prior art CN111111682A discloses a hydrotreating catalyst and a preparation method thereof. This method uses group VIII transition metals and group VIB transition metals as active components, adds an organic acid complexing agent and a surfactant to the metal salt solution to promote the dispersion of metal-organic particles in the sol form in the system, and makes the catalyst through a kneading-molding process, which can weaken the strong interaction between the active metal and the carrier, thereby improving the desulfurization and denitrification ability of the catalyst; the prior art CN111822023A discloses an active metal impregnating solution and a preparation method of a hydrotreating catalyst. This impregnating solution contains an organic solvent, an active metal salt, and an organic phosphide containing benzene and / or ester groups. Since the impregnating solution is an organic solvent, a Mo / W-Co / Ni-P solution can be prepared within a larger component content and ratio range, thereby avoiding the non-formulable range interval existing in the conventional aqueous solution impregnating solution; the prior art CN111495400A discloses a preparation method of a hydrodearomatization catalyst. This method uses modified alumina containing an acid component as a carrier, makes it into a hollow cylinder shape, first loads Mo by a batch complexing technique, and then sequentially loads W, Ni, and P after drying and dehydrating, and finally prepares the catalyst through drying and calcination. The obtained catalyst has good hydrodesulfurization, denitrification, and aromatic saturation performance, and is particularly suitable for the process of hydrotreating distillate oil with a high aromatic hydrocarbon content to produce white oil.

[0004] In the prior art, a preparation method of a supported ultrafine alloy hydrodearomatization catalyst is also disclosed. This method uses shaped monolithic or binary composite oxides such as Al2O3, Al2O3-SiO2, SiO2-TiO2, SiO2-ZrO2, etc. as carriers, with the main active components being single components such as Ni, Co or their complexes, the co-active components being Ti and Mo, and a certain amount of alkaline earth metals or rare earth metals being added as additives; the active metal loading method uses dip coating, and the active metal undergoes a sol-gel reaction in situ on the surface of the carrier, and then is aged, dried and calcined to obtain the finished catalyst; this sol-gel process on the surface of the carrier is beneficial to the ultra-finement of the metal and the carrier, can enhance the support-metal interaction (SMSI), improve the active specific surface area of the catalyst and the catalyst stability, and ultimately improve the thermal stability of the catalyst.

[0005] In the research, it is found that for the selective high-pressure hydrogenation of heavy distillate oil to remove polycyclic aromatic hydrocarbons, the effects exerted by the currently available catalysts on the market are not ideal; by studying the reaction path of aromatic hydrocarbon hydrogenation, it is found that the diffusion of aromatic hydrocarbons in the catalyst pores is the main reason for the low selectivity of aromatic hydrocarbon hydrogenation. During the diffusion process of aromatic hydrocarbons in the catalyst pores, they will be over-hydrogenated, resulting in the loss of a part of bicyclic aromatic hydrocarbons and non-toxic polycyclic aromatic hydrocarbons. In short, how to avoid the over-hydrogenation of heavy aromatic hydrocarbons and improve the selective hydrogenation performance of the catalyst for aromatic hydrocarbons is an urgent problem that needs to be solved by those skilled in the art at present.

[0006] In view of this, the present invention is specifically proposed. Summary of the Invention

[0007] One of the purposes of the present invention is to provide a preparation method of a selective hydrodearomatization catalyst for heavy distillate oil, which solves the problem of secondary hydrogenation of aromatic hydrocarbons caused by diffusion and is beneficial to improving the effect of selective hydrogenation of aromatic hydrocarbons in heavy distillate oil.

[0008] Another purpose of the present invention is to provide a selective hydrodearomatization catalyst for heavy distillate oil. Since the metal content is relatively low, a lower space velocity is required, which is beneficial to reducing the reaction temperature, thereby further improving the selectivity of aromatic hydrocarbon hydrogenation.

[0009] The third purpose of the present invention is to provide an application of a selective hydrodearomatization catalyst for heavy distillate oil, which is beneficial to the preparation of high-C A value rubber plasticizer products.

[0010] In order to achieve the above purposes of the present invention, the following technical solutions are specifically adopted:

[0011] In the first aspect, a preparation method of a selective hydrodearomatization catalyst for heavy distillate oil includes the following steps:

[0012] (a) Impregnate the catalyst support with a polymer, allowing the polymer to diffuse into the pores of the catalyst support to obtain a catalyst support treated with the polymer;

[0013] The polymer occupies one-fourth to one-half of the pores of the catalyst support;

[0014] (b) Impregnate the catalyst support treated with the polymer with a metal salt solution, followed by drying and calcination to obtain the selective hydrodearomatization catalyst for heavy distillate oil.

[0015] Furthermore, in step (a), the polymer includes a water-soluble polymer;

[0016] Preferably, the water-soluble polymer includes at least one of polyacrylamide, polyvinyl alcohol, polymaleic anhydride, polyacrylic acid, polyethylene glycol, water-soluble starch, gelatin, carboxymethyl cellulose, and hydroxyethyl cellulose.

[0017] Furthermore, the preparation method of the catalyst support includes the following steps:

[0018] Mix pseudoboehmite, an extrusion aid, nitric acid, and water to obtain a mixed material. Take the mixed material and perform shaping, drying, and calcination in sequence to obtain the catalyst support.

[0019] Furthermore, the pore volume of the pseudoboehmite is ≥1.0 mL / g, and the specific surface area is ≥300 m 2 / g;

[0020] Preferably, the extrusion aid includes at least one of sesbania powder, starch, and methyl cellulose.

[0021] Furthermore, the cross-sectional shape of the catalyst support is any one of circular, cloverleaf, or four-leaf clover.

[0022] Furthermore, in step (b), the metal salt solution contains a nickel salt and a tungsten salt;

[0023] Preferably, the nickel salt includes at least one of nickel nitrate and basic nickel carbonate;

[0024] Preferably, the tungsten salt includes at least one of ammonium tungstate, ammonium metatungstate, and ammonium paratungstate;

[0025] Preferably, the weight ratio of nickel atoms to tungsten atoms in the impregnation amounts of the nickel salt and the tungsten salt is between 1:10 and 1:6.

[0026] Furthermore, in step (b), the heating rate of the drying is ≥50 °C / hour;

[0027] Preferably, the temperature of the calcination is 400 °C to 500 °C, preferably 450 °C.

[0028] In a second aspect, a heavy fraction oil selective hydrodearomatization catalyst prepared by the preparation method described in any one of the above.

[0029] Furthermore, the heavy fraction oil selective hydrodearomatization catalyst is an eggshell-type hydrogenation catalyst;

[0030] Preferably, the eggshell thickness of the eggshell-type hydrogenation catalyst is 0.3 mm or less.

[0031] In a third aspect, an application of the heavy fraction oil selective hydrodearomatization catalyst described above in the preparation of a high-C A value rubber plasticizer.

[0032] Compared with the prior art, the present invention has at least the following beneficial effects:

[0033] The preparation method of the heavy fraction oil selective hydrodearomatization catalyst provided by the present invention can form an eggshell-type hydrogenation catalyst, solve the problem of heavy fraction oil selective hydrogenation, and solve the technical problem that the aromatics diffusing in the catalyst pores undergo secondary hydrogenation, resulting in low aromatics hydrogenation selectivity, achieving the technical effect of effectively improving the aromatics hydrogenation selectivity.

[0034] For the heavy fraction oil selective hydrodearomatization catalyst provided by the present invention, due to the low metal content, a lower space velocity is required, which is beneficial to reducing the reaction temperature, thereby further improving the aromatics hydrogenation selectivity.

[0035] The application of the heavy fraction oil selective hydrodearomatization catalyst provided by the present invention is beneficial to the preparation of a high-C A value rubber plasticizer product. Specific embodiments

[0036] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.

[0037] According to the first aspect of the present invention, a preparation method of a heavy fraction oil selective hydrodearomatization catalyst is provided, including the following steps:

[0038] (a) Impregnating the catalyst support with a high polymer to allow the high polymer to diffuse into the pores of the catalyst support, obtaining a catalyst support treated with the high polymer;

[0039] Among them, the high polymer occupies one-fourth to one-half of the pores of the catalyst support;

[0040] (b) The obtained catalyst support after treating the polymer is impregnated with a metal salt solution, and then dried and calcined to obtain a selective hydrodearomatization catalyst for heavy distillate oil.

[0041] The method of the present invention forms an eggshell-type hydrogenation catalyst, which shortens the diffusion radius of the oil product inside the catalyst, reduces the secondary hydrogenation of aromatics or reduces the hydrogenation depth of aromatics caused by slow diffusion in the catalyst pores, and achieves the technical effect of effectively improving the hydrogenation selectivity of aromatics.

[0042] In a preferred embodiment, in step (a), the polymer can be selected from water-soluble polymers; the water-soluble polymers include but are not limited to at least one of polyacrylamide, polyvinyl alcohol, polymaleic anhydride, polyacrylic acid, polyethylene glycol, water-soluble starch, gelatin, hydroxymethylcellulose, and carboxymethylcellulose.

[0043] In the present invention, after the water-soluble polymer is dissolved, a conventional equal-volume impregnation method can be used to enable the water-soluble polymer to be adsorbed into the pores of the catalyst support; the dosage of the water-soluble polymer is controlled according to the pore volume of the catalyst support, and the dry amount of the polymer can occupy one-fourth to one-half of the pores of the catalyst support; after the catalyst support is impregnated with the polymer, the drying rate can be controlled to promote the diffusion of the polymer into the interior of the catalyst support, wherein the drying temperature can be controlled between 80°C and 150°C, and its typical but non-limiting temperatures are for example 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, and the heating rate ≤ 10°C / hour.

[0044] In a preferred embodiment, the preparation method of the catalyst support includes the following steps:

[0045] Pseudoboehmite, an extrusion aid, nitric acid, and water are mixed to obtain a mixed material, and the mixed material is sequentially formed, dried, and calcined to obtain a catalyst support;

[0046] Among them, the drying temperature can be 80°C to 150°C, and its typical but non-limiting temperatures are for example 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C; the drying time can be 2h to 4h, and its typical but non-limiting times are for example 2h, 3h, 4h;

[0047] The calcination temperature can be 500°C to 750°C, and its typical but non-limiting temperatures are for example 500°C, 550°C, 600°C, 650°C, 700°C, 750°C; the calcination time can be 3h to 4h, and its typical but non-limiting times are for example 3h, 3.5h, 4h.

[0048] In the present invention, the pore volume of the pseudo-boehmite ≥ 1.0 mL / g, for example, it can be 1.0 mL / g, 1.6 mL / g, 2.0 mL / g, but is not limited to the listed values. At the same time, the specific surface area of the pseudo-boehmite ≥ 300 m 2 / g.

[0049] In a preferred embodiment, the extrusion aid includes, but is not limited to, any one or a combination of at least two of sesbania powder, starch or methyl cellulose. For example, it can be a combination of sesbania powder and starch, or a combination of starch and methyl cellulose, or a combination of sesbania powder and methyl cellulose, or a combination of sesbania powder, starch and methyl cellulose.

[0050] In a preferred embodiment, the cross-sectional shape of the catalyst support can be any one of circular, clover-shaped and / or four-leaf clover-shaped.

[0051] In a preferred embodiment, in step (b), a metal salt solution is prepared as an impregnating solution according to the weight of the catalyst active component (calculated as oxide) accounting for 15% - 22.5% of the weight of the catalyst. The nickel salt in the impregnating solution includes, but is not limited to, nickel nitrate and / or basic nickel carbonate, and the tungsten salt includes, but is not limited to, any one or a combination of at least two of ammonium tungstate, ammonium metatungstate and / or ammonium paratungstate.

[0052] In a preferred embodiment, the impregnation amounts of the nickel salt and the tungsten salt can be controlled within the range of the weight ratio of nickel atoms to tungsten atoms being 1:10 - 1:6, and the impregnation can be carried out by the equal-volume impregnation method; after the impregnation is completed, the catalyst active metal is anchored through the steps of drying and calcination; wherein, the drying can be carried out by the rapid drying method, and the heating rate during drying ≥ 50 °C / hour, which is beneficial to quickly leaving the metal salt on the outer layer of the catalyst; the calcination temperature can be 400 °C - 500 °C, and its typical but non-limiting temperatures are, for example, 400 °C, 410 °C, 420 °C, 430 °C, 440 °C, 450 °C, 460 °C, 470 °C, 480 °C, 490 °C, 500 °C, and can be further preferably 450 °C, which is more beneficial to further improving the calcination effect.

[0053] In the present invention, according to the situation of the catalyst support being treated with the water-soluble polymer, the metal content in the impregnating solution is controlled, and at the same time, the heating rate in the drying stage is controlled, so that the eggshell thickness of the catalyst can be controlled at 0.3 mm and below.

[0054] According to the second aspect of the present invention, there is provided a heavy fraction oil selective hydrode-aromatization catalyst prepared by the preparation method described in any one of the above.

[0055] The heavy fraction oil selective hydrodearomatization catalyst provided by the present invention has a low metal content, so it requires a lower space velocity, which is beneficial to reducing the reaction temperature, and thus can further improve the selectivity of aromatic hydrocarbon hydrogenation.

[0056] According to the third aspect of the present invention, there is provided an application of the above-mentioned heavy fraction oil selective hydrodearomatization catalyst in the preparation of high-C A value rubber plasticizer.

[0057] The application of the heavy fraction oil selective hydrodearomatization catalyst provided by the present invention is beneficial to the preparation of high-C A value rubber plasticizer products.

[0058] The present invention will be further described below by way of examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or directly purchased from the market.

[0059] Example 1

[0060] A preparation method of a heavy fraction oil selective hydrodearomatization catalyst includes the following steps:

[0061] (1) After mixing pseudoboehmite, an extrusion aid, nitric acid, and water, molding, drying, and calcination are carried out in sequence to obtain a catalyst carrier, and the cross-sectional shape thereof is clover-shaped;

[0062] Among them, the pore volume of pseudoboehmite is 1.6 mL / g, and the specific surface area is 350 m 2 / g; the extrusion aid is a composition of talc powder and methyl cellulose;

[0063] The drying temperature is 100 °C, and the drying time is 3 h; the calcination temperature is 600 °C, and the calcination time is 3.5 h;

[0064] (2) Treat the catalyst carrier obtained in step (1) with a water-soluble polymer and dry it. The specific steps are as follows: First, dissolve the water-soluble polymer. The polymer is polyacrylamide. Then, by the equal-volume impregnation method, the water-soluble polymer is adsorbed into the pores of the catalyst carrier. The polymer occupies one-fourth of the pores of the catalyst carrier. After impregnating the polymer, the drying rate should be strictly controlled to promote the diffusion of the polymer into the interior of the catalyst carrier. The drying temperature is 100 °C, and the heating rate of drying is ≤10 °C / hour;

[0065] (3) Mix nickel salt, tungsten salt, a competitive adsorbent, and water to prepare an impregnation solution;

[0066] Among them, the impregnation solution is prepared according to 18% of the weight of the catalyst active component (calculated as oxide) accounting for the weight of the catalyst;

[0067] The nickel salt is selected from nickel nitrate, and the tungsten salt is selected from ammonium tungstate;

[0068] Meanwhile, the impregnation amounts of the nickel salt and the tungsten salt are in a weight ratio of nickel atoms to tungsten atoms of 1:8;

[0069] (4) The catalyst support obtained in step (2) is impregnated with the impregnation solution obtained in step (3) by the equal-volume impregnation method. After the impregnation is completed, the active metal of the catalyst is anchored through the steps of drying and calcination to obtain a selective hydrogenation and de-aromatization catalyst, which is an eggshell-type hydrogenation catalyst (the eggshell thickness is 0.3 mm or less);

[0070] Among them, rapid drying is adopted for drying, and the heating rate of drying is ≥50 °C / hour, so as to quickly leave the metal salt on the outer layer of the catalyst; after drying, calcination treatment is carried out, and the calcination temperature is 450 °C.

[0071] Example 2

[0072] The difference between this example and Example 1 is only that in step (2), the polymer occupies one-third of the pores of the catalyst support;

[0073] The remaining steps and their process parameters are the same as those in Example 1, and a selective hydrogenation and de-aromatization catalyst is obtained.

[0074] Example 3

[0075] The difference between this example and Example 1 is only that in step (2), the polymer occupies one-half of the pores of the catalyst support;

[0076] The remaining steps and their process parameters are the same as those in Example 1, and a selective hydrogenation and de-aromatization catalyst is obtained.

[0077] Example 4

[0078] The difference between this example and Example 1 is only that in step (2), the polymer used is polyethylene glycol;

[0079] The remaining steps and their process parameters are the same as those in Example 1, and a selective hydrogenation and de-aromatization catalyst is obtained.

[0080] Example 5

[0081] The difference between this example and Example 1 is only that in step (2), the polymer used is hydroxymethyl cellulose or carboxymethyl cellulose;

[0082] The remaining steps and their process parameters are the same as those in Example 1, and a selective hydrogenation and de-aromatization catalyst is obtained.

[0083] Comparative Example 1

[0084] The difference between this example and Example 1 is only that in step (2), the polymer occupies one-fifth of the pores of the catalyst support;

[0085] The remaining steps and their process parameters are the same as those in Example 1, and a selective hydrogenation de-aromatization catalyst is obtained.

[0086] Compared with Example 1, the defect of this comparative example is that due to the lack of a significant reduction in the diffusion radius, the selectivity of aromatic hydrocarbon hydrogenation is relatively low.

[0087] Comparative Example 2

[0088] The difference between this example and Example 1 is only that in step (2), the polymer occupies two-thirds of the pores of the catalyst support;

[0089] The remaining steps and their process parameters are the same as those in Example 1, and a selective hydrogenation de-aromatization catalyst is obtained.

[0090] Compared with Example 1, the defect of this comparative example is that the impregnation amount of the catalyst active component is relatively low. To ensure the hydrogenation performance, it is necessary to significantly increase the catalyst loading and the reactor volume.

[0091] Test Example 1

[0092] A selective hydrogenation test of heavy distillate oil was carried out using the selective hydrogenation de-aromatization catalyst provided in Example 1, and the test operations and conditions are as follows:

[0093] Using the Suizhong 36-1 second-stage reduced crude oil as the raw material (No. A1), a high-pressure hydrogenation test was carried out. Under the conditions of a reaction pressure of 15 MPa, a reaction temperature of 330 °C, a volume space velocity of 0.25 h -1 and a hydrogen-oil volume ratio of 1000:1, the hydrogenated product oil B11 was obtained. The properties of the raw material oil and the hydrogenated product are shown in Table 1;

[0094] Using the Suizhong 36-1 second-stage reduced crude oil as the raw material (No. A1), a high-pressure hydrogenation test was carried out. Under the conditions of a reaction pressure of 15 MPa, a reaction temperature of 340 °C, a volume space velocity of 0.3 h -1 and a hydrogen-oil volume ratio of 1000:1, the hydrogenated product oil B12 was obtained. The properties of the raw material oil and the hydrogenated product are shown in Table 1;

[0095] Using the Suizhong 36-1 third-stage reduced crude oil as the raw material (No. A2), a high-pressure hydrogenation test was carried out. Under the conditions of a reaction pressure of 15 MPa, a reaction temperature of 340 °C, a volume space velocity of 0.25 h -1 and a hydrogen-oil volume ratio of 1000:1, the hydrogenated product oil B21 was obtained. The properties of the raw material oil and the hydrogenated product are shown in Table 1;

[0096] Using the cut 3 distillate oil of Suizhong 36-1 as the raw material (No. A2), a high-pressure hydrogenation test was carried out. The reaction was carried out under the conditions of a reaction pressure of 15 MPa, a reaction temperature of 345 °C, a volume space velocity of 0.3 h -1 and a hydrogen-oil volume ratio of 1000:1 to obtain the hydrogenated product oil B22. The properties of the raw material oil and the hydrogenated product are shown in Table 1.

[0097] Table 1

[0098]

[0099] Test Example 2

[0100] A selective hydrogenation test of heavy distillate oil was carried out using the selective hydrogenation de-aromatization catalyst provided in Example 2. The test operation and its conditions refer to Test Example 1. The properties of the hydrogenated product are shown in Table 2.

[0101] Table 2

[0102]

[0103] Test Example 3

[0104] A selective hydrogenation test of heavy distillate oil was carried out using the selective hydrogenation de-aromatization catalyst provided in Example 3. The test operation and its conditions refer to Test Example 1. The properties of the hydrogenated product are shown in Table 3.

[0105] Table 3

[0106]

[0107] Test Example 4

[0108] A selective hydrogenation test of heavy distillate oil was carried out using the selective hydrogenation de-aromatization catalyst provided in Example 4. The test operation and its conditions refer to Test Example 1. The properties of the hydrogenated product are shown in Table 4.

[0109] Table 4

[0110]

[0111] Test Example 5

[0112] A selective hydrogenation test of heavy distillate oil was carried out using the selective hydrogenation de-aromatization catalyst provided in Example 5. The test operation and its conditions refer to Test Example 1. The properties of the hydrogenated product are shown in Table 5.

[0113] Table 5

[0114]

[0115] As can be seen from the data results, for the selective hydrode-aromatization catalyst (egg-shell type hydrogenation catalyst) of the present invention, using the second and third reduced distillate fractions of Suizhong 36-1 as raw materials, products with a C A value above 13.5% and environmental protection indicators meeting the requirements of the national standard GB / T 33322 (Rubber plasticizer - Aromatic base mineral oil) can be obtained.

[0116] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A preparation method of a selective hydrodearomatization catalyst for heavy distillate oil, characterized in that, It includes the following steps: (a) Impregnating a catalyst support with a polymer to allow the polymer to diffuse into the pores of the catalyst support, thereby obtaining a catalyst support treated with the polymer; The polymer occupies one-fourth to one-half of the pores of the catalyst support; (b) Impregnating the catalyst support treated with the polymer with a metal salt solution, followed by drying and calcination to obtain the selective hydrodearomatization catalyst for heavy distillate oil.

2. The preparation method according to claim 1, characterized in that In step (a), the polymer includes a water-soluble polymer; Preferably, the water-soluble polymer includes at least one of polyacrylamide, polyvinyl alcohol, polymaleic anhydride, polyacrylic acid, polyethylene glycol, water-soluble starch, gelatin, carboxymethyl cellulose, and hydroxyethyl cellulose.

3. The preparation method according to claim 1 or 2, characterized in that, The preparation method of the catalyst support includes the following steps: Mixing pseudoboehmite, an extrusion aid, nitric acid, and water to obtain a mixed material, and subjecting the mixed material to shaping, drying, and calcination in sequence to obtain the catalyst support.

4. The preparation method according to claim 3, characterized in that, The pore volume of the pseudo-boehmite is ≥ 1.0 mL / g, and the specific surface area is ≥ 300 m 2 / g; Preferably, the extrusion aid includes at least one of sesbania powder, starch, and methyl cellulose.

5. The preparation method according to claim 4, characterized in that, The cross-sectional shape of the catalyst support is any one of circular, cloverleaf-shaped, or four-leaf clover-shaped.

6. The preparation method according to claim 1, wherein In step (b), the metal salt solution contains a nickel salt and a tungsten salt; Preferably, the nickel salt includes at least one of nickel nitrate and basic nickel carbonate; Preferably, the tungsten salt includes at least one of ammonium tungstate, ammonium metatungstate, and ammonium paratungstate; Preferably, the weight ratio of nickel atoms to tungsten atoms in the impregnation amounts of the nickel salt and the tungsten salt is between 1:10 and 1:

6.

7. The preparation method according to claim 1, wherein In step (b), the heating rate of the drying is ≥50 °C / hour; Preferably, the temperature of the calcination is 400 °C to 500 °C, preferably 450 °C.

8. A selective hydrodearomatization catalyst for heavy distillate oil prepared by the preparation method according to any one of claims 1-7.

9. The selective hydrodearomatization catalyst for heavy distillate oil according to claim 8, characterized in that, The selective hydrodearomatization catalyst for heavy distillate oil is an eggshell-type hydrogenation catalyst; Preferably, the eggshell thickness of the eggshell-type hydrogenation catalyst is 0.3 mm or less.

10. Use of the heavy fraction oil selective hydrode-aromatization catalyst according to claim 8 or 9 in the preparation of a high C A -value rubber plasticizer.

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