A petroleum resin hydrogenation catalyst and a preparation method thereof

Abstract

The present application provides a petroleum resin hydrogenation catalyst, comprising a carrier, an active component Ni, a first additive metal and a second additive metal, the first additive metal is Mo and / or W, and the second additive metal is selected from at least one of Zn, Cu, Mg, Ca and La. The catalyst is obtained by loading the first additive metal, drying, reduction, loading Ni again, drying in an inert atmosphere, loading the second additive metal again, drying in an inert atmosphere, reduction. Through the specific preparation process, the active components and additives can be fully reduced, and the dispersion of low-temperature reduced Ni is high, which is conducive to promoting the interaction between reduced Mo and / or W and reduced Ni, fully playing the hydrogenation activity, and the second additive is mainly located on the surface of the reduced Ni, which can modify the high active site, improve the sulfur resistance of the catalyst and inhibit the sintering of the catalyst, thereby improving the overall activity and stability of the catalyst.

Description

Technical Field

[0001] This invention relates to the field of petroleum hydrogenation technology, specifically to a petroleum resin hydrogenation catalyst and its preparation method. Background Technology

[0002] As the scale of ethylene plants in my country continues to expand, the amount of C5 byproducts is also increasing. The main utilization method is the production of C5 petroleum resin, which is then saturated with double bonds through catalytic hydrogenation to remove residual sulfur and halogens, yielding hydrogenated C5 petroleum resin. The hydrogenation process improves the resin's color and photothermal stability. Hydrogenated C5 petroleum resin, as a high-value-added product, is widely used in the fine chemical industry, significantly increasing economic benefits. Therefore, accelerating research on catalysts and processes for C5 hydrogenated petroleum resin is essential.

[0003] CN114570363A discloses a method for preparing a noble metal-based petroleum resin hydrogenation catalyst. The active metal is at least one of Pd or Pt, the noble metal loading is 0.01-5%, the support is ZnTiO3 modified with an alkali metal, and the additive is a boron oxide. This catalyst can maintain a high conversion rate for C5 petroleum resin while producing a product with a high softening point. However, because this catalyst uses a noble metal active component, it is expensive and sensitive to impurities, which affects its stability.

[0004] CN109482189A discloses a method for preparing a nickel-based C5 petroleum resin hydrogenation catalyst. The catalyst uses aluminum isopropoxide and isopropanol solution as the reaction substrate, zirconium and magnesium as additives, nickel as the catalytic active component, and an organic surfactant as a dispersant. Nickel accounts for 40-60% of the catalyst mass, while zirconium and magnesium account for 1-15%. This catalyst uses a high nickel content as the active component, which can lead to the aggregation and growth of nickel grains, resulting in a decrease in the number of active centers and thus a decline in catalyst activity.

[0005] CN109395738A discloses a method for preparing a catalyst for the hydrogenation of C5 petroleum resin, using an alumina-silica composite support, with nickel oxide, molybdenum oxide, and magnesium oxide as active components. The catalyst contains 3–20% nickel oxide, 2–18% molybdenum oxide, and 0.1–6.5% magnesium oxide. In this catalyst, the active metals are simultaneously impregnated on the support. Before the reaction, the active metals exist in an oxidized state. However, nickel oxide is more easily reduced than molybdenum oxide, weakening the interaction between metallic nickel and tungsten, thus reducing the catalyst activity. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a petroleum resin hydrogenation catalyst and its preparation method. The catalyst of this invention exhibits high hydrogenation activity and stability, and can be applied to petroleum resin hydrogenation processes, particularly suitable for C5 petroleum resin hydrogenation.

[0007] The technical objective of the first aspect of this invention is to provide a petroleum resin hydrogenation catalyst, comprising a support, an active component Ni, a first auxiliary metal and a second auxiliary metal, wherein the first auxiliary metal is Mo and / or W, and the second auxiliary metal is selected from at least one of Zn, Cu, Mg, Ca, and La.

[0008] Furthermore, based on the total weight of the catalyst, Ni content is 5-20% (based on elemental composition), preferably 8-15%; the first additive content is 3%-15% (based on elemental composition), preferably 5-10%; the second additive metal content is 0.5%-5% (based on elemental composition), preferably 1-4%, with the remainder being a carrier.

[0009] Furthermore, the carrier is an inorganic refractory oxide, specifically, selected from at least one oxide of elements in Group II, Group III, Group IV and Group IVB of the periodic table, more specifically, selected from at least one of silicon dioxide and aluminum oxide, with aluminum oxide being the most preferred.

[0010] Furthermore, the carrier is aluminum oxide with a carbon inert surface layer.

[0011] Furthermore, the carbon inert surface layer is formed by impregnating a carrier with an impregnation liquid containing organic additives and then heat-treating it in an inert atmosphere.

[0012] Furthermore, the organic auxiliary agent is an alcohol or organic acid containing 2-10 carbon atoms and hydroxyl and / or carboxyl groups. Specifically, it is selected from at least one of ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, malonic acid, succinic acid, and glutaric acid. The amount of the organic auxiliary agent added is 2-10 wt% of the carrier weight, preferably 3-8 wt%.

[0013] The second aspect of this invention aims to provide a method for preparing a petroleum resin hydrogenation catalyst, comprising:

[0014] (l) The first auxiliary metal is loaded onto a support, dried, and reduced to obtain catalyst precursor A;

[0015] (2) Ni was supported on catalyst precursor A and dried under an inert atmosphere to obtain catalyst precursor B;

[0016] (3) The second auxiliary metal is loaded onto catalyst precursor B, dried and reduced under an inert atmosphere to obtain the petroleum resin hydrogenation catalyst.

[0017] Furthermore, the load described in the above steps is loaded by impregnation, preferably by equal volume impregnation; the carrier or precursor is impregnated with a solution containing metal salts.

[0018] Furthermore, when using the impregnation method for loading in step (1), it is preferable to add an organic additive to the impregnation solution to increase the dispersion of the metal. The organic additive is an alcohol or organic acid containing 2-10 carbon atoms and hydroxyl and / or carboxyl groups. Specifically, it is selected from at least one of ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, malonic acid, succinic acid, and glutaric acid. The amount of the organic additive added is 2-10 wt% of the carrier weight, preferably 3-8 wt%.

[0019] Furthermore, the preparation method of the impregnation solution containing the first auxiliary metal in step (1) is well known to those skilled in the art. For example, nitrates, acetates or sulfates of the first auxiliary metal are generally used, and an equal volume impregnation method can be adopted.

[0020] Furthermore, the drying conditions described in step (1) are: drying temperature 40-90℃, drying time 3-6 hours.

[0021] Furthermore, the reduction in step (1) is carried out in a hydrogen atmosphere at a pressure of 0.1–4.0 MPa, a reduction temperature of 400–550 °C, and a reduction time of 3–12 h.

[0022] Furthermore, the preparation method of the Ni-containing impregnation solution in step (2) is well known to those skilled in the art. For example, Ni nitrate, acetate or sulfate solutions are generally used, and an equal volume impregnation method can be adopted.

[0023] Furthermore, the inert atmosphere described in steps (2) and (3) includes, but is not limited to, at least one of nitrogen, helium, argon and neon; the drying temperature described in steps (2) and (3) is 90 to 150°C, and the drying time is 4 to 16 hours.

[0024] Furthermore, the preparation method of the impregnation solution containing the second auxiliary metal in step (3) is well known to those skilled in the art. For example, a solution of nitrate, acetate or sulfate of the second auxiliary metal is generally used, and an equal volume impregnation method can be adopted.

[0025] Furthermore, the reduction in step (3) is carried out in a hydrogen atmosphere at a pressure of 0.1 to 4.0 MPa, a reduction temperature of 200 to 300°C, and a reduction time of 3 to 24 hours.

[0026] Furthermore, the catalyst prepared by this invention is a reduced catalyst, and the finished catalyst needs to be stored in an inert atmosphere.

[0027] The technical objective of the third aspect of this invention is to provide a method for hydrogenating petroleum resin, wherein the above-mentioned catalyst is used to react with the petroleum resin.

[0028] Furthermore, the reaction is carried out in a fixed-bed reactor at a temperature of 200–240°C, a pressure of 4.0–15.0 MPa, and a space velocity of 0.3–2.5 h⁻¹. -1 The molar ratio of unsaturated hydrocarbons to hydrogen in petroleum resin is 1:3 to 1:4. During the hydrogenation reaction, the solvent is any one or more of cyclohexane, cyclopentane, toluene, or xylene, preferably toluene or xylene, and the weight ratio of raw material to solvent is 1:1 to 1:2.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] (1) The catalyst of the present invention uses Ni as the main active component and adds a first auxiliary metal and a second auxiliary metal. The several metal components work together to increase the activity of the catalyst.

[0031] (2) On the one hand, since the oxides of the first auxiliary metal Mo and / or W are difficult to reduce, while Ni is easier to reduce, the high temperature during the reduction process before use of the non-reduced catalyst can easily cause the reduced Ni to aggregate, which prevents Ni from fully exerting its hydrogenation activity and thus reduces the catalyst activity. On the other hand, since the amount of the second auxiliary metal is small, it is easily covered by the high content of Ni and the first auxiliary metal, making it difficult to fully exert the auxiliary role to improve the catalyst's resistance to sulfur poisoning and inhibit nickel sintering. To address the above problems, the inventors used a stepwise impregnation and reduction method with different active metals. First, Mo and / or W metals were impregnated on the support and reduced at high temperature beforehand. Then, Ni was impregnated, and then the second auxiliary metal was impregnated and reduced at low temperature to obtain the petroleum resin hydrogenation catalyst. The above process not only allows each active component and auxiliary to be fully reduced, but also results in a higher dispersion of Ni after low-temperature reduction, which is beneficial to promote the interaction between the reduced Mo and / or W and the reduced Ni, thus fully exerting the hydrogenation activity. Furthermore, the second auxiliary is mainly located on the surface of the reduced Ni, which can modify the high-activity sites, improve the catalyst's resistance to sulfur, and inhibit catalyst sintering, thereby improving the overall activity and stability of the catalyst.

[0032] (3) In the preferred preparation method, the catalyst is prepared by pretreating the support with organic additives and the first additive metal, loading the active metal Ni, and loading the second additive metal. The organic additives and the first additive metal can modify the highly active sites on the support surface, weaken the interaction between Ni and the support, and improve the dispersion of Ni. Furthermore, through the treatment in step (1), the organic additives form an inert carbon surface layer on the support surface, which allows Ni to interact more with the additive metal, making it more conducive to exerting the synergistic effect of the additive metal and improving the activity of the catalyst. The non-polar inert carbon surface layer formed by the organic additives is conducive to the adsorption of non-polar petroleum resin molecules on the catalyst surface, and modifies the acidic sites on the surface, reducing the surface acidity, weakening the rearrangement and cracking reaction of resin molecules, and maintaining the softening point.

[0033] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0034] The method of the present invention will be further described in detail below through embodiments. These embodiments are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0035] Analytical Instruments and Standards: Color Value: HunterLab Colour Quest EX colorimeter (USA), ASTM E313 standard. Bromine Value: METTLER TOLEDO DL58 titrator (USA), ASTM D1159-93 standard. Softening Point: SYD-2806F softening point tester (China), GB / T 12007.6-1989 standard. Chlorine Content: RPA-200A microcoulometric analyzer (China), SHT 1757-2006 standard.

[0036] Example 1

[0037] (1) An equal volume of an aqueous solution containing ammonium heptamolybdate and acetic acid (containing 5% of the carrier weight) was impregnated into an alumina support, dried at 90°C for 3 hours, and then reduced at 450°C for 5 hours in an H2 atmosphere to obtain catalyst precursor A.

[0038] (2) The solution containing nickel nitrate is impregnated into the catalyst precursor A prepared in step (1), and then dried at 120°C for 3 hours under N2 atmosphere to obtain catalyst precursor B.

[0039] (3) The zinc nitrate solution was impregnated into the catalyst precursor B prepared in step (2), and then dried at 110°C for 3 hours under N2 atmosphere. Then, hydrogen was used for reduction treatment at a reduction temperature of 300°C, a reduction pressure of 2.0 MPa, and a reduction time of 5 hours to obtain catalyst C-1.

[0040] The weight percentages of the components in catalyst C-1 are as follows: Ni 15.1%, Mo 6.0%, Zn 3.1%, and the remainder is alumina support.

[0041] Example 2

[0042] (1) An equal volume of an aqueous solution containing ammonium metatungstate and citric acid (6% of the carrier weight) was impregnated into an alumina support, dried at 80°C for 4 hours, and then reduced at 500°C for 4 hours in an H2 atmosphere to obtain catalyst precursor A.

[0043] (2) The solution containing nickel nitrate is impregnated into the catalyst precursor A prepared in step (1), and then dried at 120°C for 3 hours under N2 atmosphere to obtain catalyst precursor B.

[0044] (3) The copper acetate solution was impregnated into the catalyst precursor B prepared in step (2), and then dried at 140°C for 3 hours under N2 atmosphere. Then, hydrogen was used for reduction treatment at a reduction temperature of 260°C, a reduction pressure of 3.0 MPa, and a reduction time of 5 hours to obtain catalyst C-2.

[0045] The weight percentages of the components in catalyst C-2 are as follows: Ni 10.0%, W 9.1%, Cu 2.5%, and the remainder is alumina support.

[0046] Example 3

[0047] (1) An equal volume of an aqueous solution containing ammonium heptamolybdate and glycerol (4% of the carrier weight) was impregnated into an alumina support, dried at 90°C for 3 hours, and then reduced at 450°C for 5 hours in an H2 atmosphere to obtain catalyst precursor A.

[0048] (2) The nickel nitrate solution was impregnated into the catalyst precursor A prepared in step (1), and then dried at 100°C for 5 h under N2 atmosphere to obtain catalyst precursor B.

[0049] (3) The magnesium nitrate solution was impregnated into the catalyst precursor B prepared in step (2), and then dried at 110°C for 6 hours under N2 atmosphere. Then, hydrogen was used for reduction treatment at a reduction temperature of 240°C, a reduction pressure of 1.0 MPa, and a reduction time of 4 hours to obtain catalyst C-3.

[0050] The weight percentages of the components in catalyst C-3 are as follows: Ni 12.0%, Mo 8.1%, Mg 2.0%, and the remainder is alumina support.

[0051] Example 4

[0052] (1) An equal volume of an aqueous solution containing ammonium metatungstate and ethylene glycol (containing 8% of the weight of the support) was impregnated into an alumina support, dried at 70°C for 6 hours, and then reduced at 500°C for 4 hours in an H2 atmosphere to obtain catalyst precursor A.

[0053] (2) The nickel nitrate solution was impregnated into the catalyst precursor A prepared in step (1), and then dried at 110°C for 4 hours under N2 atmosphere to obtain catalyst precursor B.

[0054] (3) The calcium nitrate solution was impregnated into the catalyst precursor B prepared in step (2), and then dried at 130°C for 5 hours under N2 atmosphere. Then, hydrogen was used for reduction treatment at a reduction temperature of 280°C, a reduction pressure of 2.0 MPa, and a reduction time of 6 hours to obtain catalyst C-4.

[0055] The weight percentages of the components in catalyst C-4 are as follows: Ni 8.1%, W 10.0%, Ca 2.0%, and the remainder is alumina support.

[0056] Example 5

[0057] (1) An equal volume of an aqueous solution containing ammonium heptamolybdate and malonic acid (containing 5% of the weight of the support) was impregnated into an alumina support, dried at 80°C for 5 hours, and then reduced at 500°C for 4 hours in an H2 atmosphere to obtain catalyst precursor A.

[0058] (2) The nickel nitrate solution was impregnated into the catalyst precursor A prepared in step (1), and then dried at 120°C for 5 h under N2 atmosphere to obtain catalyst precursor B.

[0059] (3) The lanthanum acetate solution was impregnated into the catalyst precursor B prepared in step (2), and then dried at 140°C for 6 hours under N2 atmosphere. Then, hydrogen was used for reduction treatment at a reduction temperature of 300°C, a reduction pressure of 3.0 MPa, and a reduction time of 3 hours to obtain catalyst C-5.

[0060] The weight percentages of the components in catalyst C-3 are as follows: Ni 12.2%, Mo 10.1%, La 3.5%, and the remainder is alumina support.

[0061] Comparative Example 1

[0062] (1) An equal volume of an aqueous solution containing ammonium heptamolybdate, acetic acid (5% of the carrier weight), and nickel nitrate was impregnated into an alumina support, dried at 90°C for 3 hours, and then reduced at 450°C for 5 hours in an H2 atmosphere to obtain a catalyst precursor.

[0063] (2) The zinc nitrate solution was impregnated into the catalyst precursor prepared in step (1), and then dried at 110°C for 3 hours under N2 atmosphere. Then, hydrogen was used for reduction treatment at a reduction temperature of 300°C, a reduction pressure of 2.0 MPa, and a reduction time of 5 hours to obtain catalyst DC-1.

[0064] The weight percentages of the components in catalyst DC-1 are as follows: Ni 15.1%, Mo 6.0%, Zn 3.0%, and the remainder is alumina support.

[0065] Comparative Example 2

[0066] (1) An equal volume of an aqueous solution containing ammonium heptamolybdate and acetic acid (5% of the carrier weight) was impregnated into an alumina support, dried at 90°C for 3 hours, and then reduced at 450°C for 5 hours in an H2 atmosphere to obtain a catalyst precursor.

[0067] (2) The solution of nickel nitrate and zinc nitrate was impregnated into the catalyst precursor prepared in step (1), and then dried at 120°C for 3 hours under N2 atmosphere. Then, hydrogen was used for reduction treatment at a reduction temperature of 300°C, a reduction pressure of 2.0 MPa, and a reduction time of 5 hours to obtain catalyst DC-2.

[0068] The weight percentages of the components in catalyst DC-2 are as follows: Ni 15.1%, Mo 6.0%, Zn 3.1%, and the remainder is alumina support.

[0069] Comparative Example 3

[0070] (1) An equal volume of an aqueous solution containing ammonium heptamolybdate and acetic acid (5% of the carrier weight) was impregnated into an alumina support, dried at 90°C for 3 hours, and then calcined at 450°C for 5 hours in an air atmosphere to obtain a catalyst precursor.

[0071] (2) The nickel nitrate solution was impregnated into the catalyst precursor A prepared in step (1), and then dried at 120°C for 3 hours in air atmosphere to obtain catalyst precursor B.

[0072] (3) The zinc nitrate solution was impregnated into the catalyst precursor B prepared in step (2), and then dried at 110°C for 3 hours in an air atmosphere. Then, hydrogen was used for reduction treatment at a reduction temperature of 300°C, a reduction pressure of 2.0 MPa, and a reduction time of 5 hours to obtain catalyst DC-3.

[0073] The weight percentages of the components in catalyst DC-3 are as follows: Ni 15.1%, Mo 6.1%, Zn 3.0%, and the remainder is alumina support.

[0074] Example 6

[0075] This example illustrates the performance of the catalyst provided by the present invention in the hydrogenation reaction of petroleum resins.

[0076] The petroleum resin used for evaluation was a commercially available mixed C5 petroleum resin. The commercially available mixed C5 petroleum resin was dissolved in cyclohexane solvent to form a raw material solution with a concentration of 40% (wt), in which the chlorine content was 3472 ppm and the sulfur content was 50.9 ppm.

[0077] The hydrogenation performance of catalysts C-1 to C-5 and comparative examples DC-1 to DC-3 was evaluated using a 200 mL fixed-bed petroleum resin hydrogenation apparatus.

[0078] The evaluation reaction conditions were: reaction temperature 220℃, operating pressure 6.0 MPa, and feed volume hourly space velocity 1 h⁻¹. -1 With a hydrogen-to-oil volume ratio of 300, after 300 hours of reaction, the reaction mixture was first washed with alkali and water, and then the solvent and by-products were removed by a falling film evaporator to obtain a solid resin product. The results of analysis and testing of the color value, chlorine content, bromine value and softening point of the raw materials and the product after each catalyst treatment are shown in Table 1.

[0079] Table 1 Catalyst Evaluation Results

[0080] Catalyst number Color values ​​(Gardner) Chlorine content (ppm) Bromine value (gBr / 100g) Softening point (°C) raw material 8.62 3472 68.1 115 C-1 0.36 5.50 0.72 101 C-2 0.53 5.72 0.94 98 C-3 0.45 4.33 0.89 105 C-4 0.44 4.84 0.98 99 C-5 0.49 4.03 0.69 105 DC-1 3.45 13.11 5.50 96 DC-2 4.05 18.55 8.68 93 DC-3 3.71 16.73 7.46 90

[0081] The evaluation results in Table 1 demonstrate that the petroleum resin hydrogenation catalyst of the present invention exhibits high hydrogenation activity, resistance to impurity poisoning, and stability in the petroleum resin hydrogenation reaction.

Claims

1. A method for preparing a petroleum resin hydrogenation catalyst, comprising: (l) The first auxiliary metal is supported on alumina, dried, and reduced. The reduction is carried out in a hydrogen atmosphere at a pressure of 0.1~4.0 MPa, a reduction temperature of 400~550℃, and a reduction time of 3~12 h to obtain catalyst precursor A. (2) Ni was supported on catalyst precursor A and dried under an inert atmosphere to obtain catalyst precursor B; (3) The second auxiliary metal is supported on catalyst precursor B, dried and reduced under an inert atmosphere to obtain the petroleum resin hydrogenation catalyst; The loading in each step is carried out by impregnation, in which the alumina or precursor is impregnated with a solution containing metal salts; In step (1), an organic additive is added to the impregnation solution. The organic additive is selected from at least one of ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, malonic acid, succinic acid, and glutaric acid. The amount of the organic additive added is 2-10 wt% of the weight of alumina. The prepared petroleum resin hydrogenation catalyst includes a support, an active component Ni, a first auxiliary metal, and a second auxiliary metal. The support is alumina with a carbon inert surface layer. The first auxiliary metal is Mo and / or W, and the second auxiliary metal is selected from at least one of Zn, Cu, Mg, Ca, and La. Based on the total weight of the catalyst, Ni has a content of 5-20% by elemental weight, the first auxiliary metal has a content of 3%-15% by elemental weight, the second auxiliary metal has a content of 0.5%-5% by elemental weight, and the balance is the support.

2. The preparation method according to claim 1, characterized in that, The amount of the organic additive added is 3 to 8 wt% of the weight of alumina.

3. The preparation method according to claim 1, characterized in that, The drying conditions described in step (1) are: drying temperature 40-90℃, drying time 3-6 hours.

4. The preparation method according to claim 1, characterized in that, The drying temperature in steps (2) and (3) is 90~150℃, and the drying time is 4~16 hours.

5. The preparation method according to claim 1, characterized in that, The reduction in step (3) is carried out in a hydrogen atmosphere at a pressure of 0.1 to 4.0 MPa, a reduction temperature of 200 to 300°C, and a reduction time of 3 to 24 hours.

6. A method for hydrogenating petroleum resin, comprising reacting the catalyst prepared according to claim 1 with the petroleum resin.

7. The method according to claim 6, characterized in that, The reaction is carried out in a fixed-bed reactor at a temperature of 200–240°C, a pressure of 4.0–15.0 MPa, and a space velocity of 0.3–2.5 h⁻¹. -1 The molar ratio of unsaturated hydrocarbons to hydrogen in petroleum resin is 1:3 to 1:4.