阅读说明：本技术 一种石油树脂加氢催化剂及其制备方法 (Petroleum resin hydrogenation catalyst and preparation method thereof ) 是由 刘丽 段为宇 姚运海 杨成敏 李扬 郭蓉 周勇 孙进 丁莉 郑步梅 于 2019-10-25 设计创作，主要内容包括：本发明公开了一种石油树脂加氢催化剂及其制备方法。石油树脂加氢催化剂,包括加氢活性组分和载体,加氢活性组分为第VIII族金属硫化物和第VIB族金属氧化物；以催化剂的总重量为基准,第VIII族金属硫化物计为3wt%-20wt%,第VIB族金属氧化物为2wt%-15wt%。石油树脂加氢催化剂的制备方法,包括如下内容：(l)用含第VIII族金属的浸渍液浸渍加氢催化剂载体,然后干燥处理,干燥后的物料进行硫化处理,得到催化剂前体；(2)用含第VIB族金属的浸渍液浸渍催化剂前体,然后在惰性气氛下,进行干燥和焙烧,得到石油树脂加氢催化剂。本发明催化剂应用于石油树脂加氢过程,具有较高抗硫、抗氯中毒的能力。(The invention discloses a petroleum resin hydrogenation catalyst and a preparation method thereof. The petroleum resin hydrogenation catalyst comprises hydrogenation active components and a carrier, wherein the hydrogenation active components are VIII group metal sulfide and VIB group metal oxide; based on the total weight of the catalyst, the amount of the VIII group metal sulfide is 3wt% -20wt%, and the amount of the VIB group metal oxide is 2wt% -15 wt%. The preparation method of the petroleum resin hydrogenation catalyst comprises the following steps: (l) Dipping a hydrogenation catalyst carrier by using dipping liquid containing VIII group metal, then drying, and vulcanizing the dried material to obtain a catalyst precursor; (2) and (3) impregnating the catalyst precursor with an impregnating solution containing VIB group metal, and then drying and roasting in an inert atmosphere to obtain the petroleum resin hydrogenation catalyst. The catalyst of the invention is applied to the hydrogenation process of petroleum resin and has higher sulfur and chlorine poisoning resistance.)

1. The petroleum resin hydrogenation catalyst is characterized by comprising a hydrogenation active component and a hydrogenation catalyst carrier, wherein the hydrogenation active component comprises a VIII group metal sulfide and a VIB group metal oxide, the VIII group metal sulfide accounts for 3wt% -20wt%, preferably 10wt% -20wt%, the VIB group metal oxide accounts for 2wt% -15wt%, preferably 3wt% -10wt%, and the hydrogenation catalyst carrier accounts for 65% -95%.

2. The catalyst of claim 1, wherein: the VIII group metal is Co and/or Ni, and the VIB group metal is Mo and/or W.

3. The catalyst of claim 1, wherein: the catalyst is analyzed by XPS energy spectrum, and the molar proportion of the sulfurized state content of the VIII group metal with the +2 valence state to the total VIII group metal content is 80-100%.

4. The catalyst of claim 1, wherein: after the catalyst is vulcanized, CO-FTIR infrared spectrum analysis is adopted, and the molar proportion of the VIB group metal-VIII group metal-S species content mol in the total VIB group metal content mol is 60-100%.

5. The catalyst of claim 1, wherein: the hydrogenation catalyst carrier component is porous inorganic refractory oxide, and is selected from one or more of oxides of elements in II group, III group, IV group and IVB group of the periodic table.

6. The catalyst of claim 1, wherein: the hydrogenation catalyst carrier component is one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, silicon magnesium oxide or aluminum magnesium oxide.

7. The catalyst of claim 1, wherein: the hydrogenation catalyst carrier component is modified by one or more of B, P or F, and the weight percentage of the modified element is 0.5-10 wt% based on the weight of the modified hydrogenation catalyst carrier component.

8. A method for preparing a petroleum resin hydrogenation catalyst according to any one of claims 1 to 6, characterized by comprising the following steps: (l) Dipping a hydrogenation catalyst carrier by using dipping liquid containing VIII group metal, then drying, and vulcanizing the dried material to obtain a catalyst precursor; (2) and (2) impregnating the catalyst precursor obtained in the step (1) with an impregnating solution containing VIB group metals, and then drying and roasting in an inert atmosphere to obtain the petroleum resin hydrogenation catalyst.

9. The method of claim 8, wherein: the first step in the dipping solution of the step (1)The mass concentration of the group metal oxide is 0.1 g/mL-1.2 g/mL, and an equal-volume impregnation mode is adopted.

10. The method of claim 8, wherein: the drying conditions in the step (1) are as follows: the drying temperature is 90-300 ℃, and the drying time is 3-6 hours.

11. The method of claim 8, wherein: the vulcanization treatment in the step (1) adopts dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 2.5-6.4 MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

12. The method of claim 8, wherein: the mass concentration of the VIB group metal oxide in the impregnation liquid in the step (2) is 0.1-1.0 g/mL.

13. The method of claim 8, wherein: the inert atmosphere in the step (2) is N₂And inert gasOne or more of the bodies; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.

14. The application of the petroleum resin hydrogenation catalyst of any one of claims 1 to 6 in the hydrogenation reaction of petroleum resin.

15. Use according to claim 14, characterized in that: carrying out a hydrogenation reaction of petroleum resin in a fixed bed reactor at the reaction temperature of 200-220 ℃; the reaction pressure is 4.0-15.0 MPa, and the volume space velocity of the reaction raw material is 0.25-2.5 h^-1(ii) a The molar ratio of unsaturated hydrocarbon to hydrogen in the petroleum resin is 1: 3-1: 4; the solvent is any one or more of cyclohexane, cyclopentane, toluene or xylene, and the weight ratio of the raw material to the solvent is 1: 1-1: 2.

Technical Field

The invention relates to a petroleum resin hydrogenation catalyst and a preparation method thereof.

Background

C₅Hydrogenated petroleum resin is prepared by reacting C under the action of hydrogenation catalyst₅The double bonds in the petroleum resin are saturated and the residual halogen elements in the polymerization process of the resin are removed to prepare the resin. The hydrogenation process improves the chroma and the photo-thermal stability of the resin and greatly widens C₅The application field of petroleum resin. C₅Hydrogenation of petroleum resin will be China C₅The petroleum resin realizes the important ways of serialization and commercialization, and is also an important means for improving economic benefits; thus, C is accelerated₅Research and development of hydrogenated petroleum resins are essential.

CN 102935367B discloses a₅A petroleum resin hydrogenation catalyst and a preparation method thereof. The catalyst comprises an alumina-titania composite carrier and metallic palladium and metallic molybdenum or metallic tungsten supported on the composite carrier. The catalyst is used in₅The petroleum resin hydrogenation process not only has low-temperature hydrogenation activity, but also has good impurity resistance and good stability. However, the catalyst adopts noble metal active components, the sulfur resistance and chlorine poisoning resistance of the catalyst are poor, the catalyst is easy to be poisoned and inactivated, and meanwhile, the catalyst adopts noble metals and is expensive.

CN 101700494B discloses the preparation and use of a hydrogenation catalyst. The catalyst adopts aluminum hydroxide, diatomite, a pore-expanding agent and rare earth element modified aluminum trioxide as carriers, bi-component noble metal loading is carried out on the carriers, and simultaneously, rare earth elements are used for carrying out catalytic activity blending to obtain a hydrogenation catalyst with high activity and long service life, so that hydrogenated petroleum resin with light hue and high softening point can be prepared. But the catalyst has poor capability of resisting sulfur and poisoning, is easy to be poisoned and deactivated, and simultaneously adopts noble metal, so the cost is high.

CN 107876049A discloses a petroleum resin hydrogenation catalyst with sulfur resistance, a preparation method and application thereof. The catalyst is prepared from alumina sol serving as a raw material by adopting a multi-time slurry dipping method₂O₃The membrane-coated active carbon carrier is then immersed in gamma-Al by the equal volume immersion method₂O₃Active component palladium and catalyst surface modifier CeO are loaded on membrane-coated active carbon carrier₂And drying and roasting to obtain the petroleum resin hydrogenation catalyst. The catalyst of the invention is particularly suitable for use in C₅The petroleum resin hydrogenation decoloring process has better activity stability and sulfur resistance effect. However, the catalyst adopts a multi-time slurry dipping method to prepare the carrier, so that the specific surface area of the catalyst is reduced, the number of active digits of the catalyst is reduced, and the activity of the catalyst is reduced.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a petroleum resin hydrogenation catalyst and a preparation method thereof. The catalyst has higher hydrogenation activity and stability, is applied to the hydrogenation process of petroleum resin, and has high capability of resisting impurity poisoning such as sulfur, chlorine and the like.

The petroleum resin hydrogenation catalyst comprises hydrogenation active components and a hydrogenation catalyst carrier, wherein the hydrogenation active components are VIII group metal sulfides and VIB group metal oxides, the VIII group metal is preferably Co and/or Ni, and the VIB group metal is preferably Mo and/or W; based on the total weight of the catalyst, the content of the VIII group metal sulfide is 3wt% -20wt%, preferably 10wt% -20wt%, the content of the VIB group metal oxide is 2wt% -15wt%, preferably 3wt% -10wt%, and the content of the hydrogenation catalyst carrier is 65% -95%.

The catalyst is analyzed by XPS energy spectrum, and the molar proportion of the sulfurized state content of the VIII group metal with the +2 valence state to the total VIII group metal content is 80-100%.

After the catalyst is vulcanized, CO-FTIR infrared spectrum analysis is adopted, and the molar proportion of the content of VIB group metal-VIII group metal-S species (such as Mo-Co-S, Mo-Ni-S, W-Co-S, W-Ni-S and the like) to the total VIB group metal content is 60-100%. The vulcanization treatment conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

The hydrogenation catalyst carrier component is one or more of porous inorganic refractory oxides selected from the oxides of elements in the II group, the III group, the IV group and the IVB group in the periodic table, more preferably one or more of silica, alumina, magnesia, zirconia, titania, silica-alumina, magnesia-silica and alumina-magnesia, and further preferably alumina. The hydrogenation catalyst carrier component can be modified according to the need, for example, modification elements such as B, P, F are adopted for modification, and the weight percentage of the modification elements is 0.5wt% -10wt% based on the weight of the modified hydrogenation catalyst carrier component.

The invention provides a preparation method of a petroleum resin hydrogenation catalyst, which comprises the following steps:

(l) Dipping a hydrogenation catalyst carrier by using dipping liquid containing VIII group metal, then drying, and vulcanizing the dried material to obtain a catalyst precursor;

(2) and (2) impregnating the catalyst precursor obtained in the step (1) with an impregnating solution containing a VIB group metal, and then drying and roasting the catalyst precursor in an inert atmosphere to obtain the petroleum resin hydrogenation catalyst.

In the method of the present invention, the second step described in step (1)The impregnation of the group metals is well known to those skilled in the art and typically involves the use of nitrate, acetate, sulfate solutions and the likeThe mass concentration of the group metal oxide is 0.1 g/mL-1.2 g/mL, an equal volume impregnation mode can be adopted, and the second step isThe group metals are preferably Ni and/or Co.

In the method of the invention, the drying conditions in the step (1) are as follows: the drying temperature is 90-300 ℃, and the drying time is 3-6 hours.

In the method of the present invention, the vulcanization treatment in step (1) is well known to those skilled in the art, and usually adopts dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide; the vulcanization pressure is 2.5-6.4 MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

In the method, the preparation method of the group VIB metal impregnation liquid in the step (2) is well known by those skilled in the art, for example, a phosphate or ammonium salt solution is generally adopted, and the mass concentration of the group VIB metal oxide in the impregnation liquid is 0.1 g/mL-1.0 g/mL. The group VIB metal is preferably Mo and/or W.

In the method of the invention, the inert atmosphere in the step (2) is N₂And an inert gas; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.

The petroleum resin hydrogenation catalyst is applied to the hydrogenation process of petroleum resin, and is particularly suitable for C₅Petroleum resin hydrogenation process.

The hydrogenation catalyst of the invention needs to be vulcanized before application, and the general vulcanization conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 2.0-6.4 MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

The invention provides application of the petroleum resin hydrogenation catalyst obtained by the preparation method, and when the petroleum resin hydrogenation catalyst is used in the hydrogenation reaction of petroleum resin, the reaction is carried out in a fixed bed reactor, and the reaction temperature is 200-220 ℃; the reaction pressure is 4.0-15.0 MPa, and the volume space velocity of the reaction raw material is 0.25-2.5 h^-1(ii) a The molar ratio of unsaturated hydrocarbon to hydrogen in the petroleum resin is preferably 1: 3-1: 4. during hydrogenation reaction, the solvent is any one or more of cyclohexane, cyclopentane, toluene or xylene, preferably toluene or xylene, and the weight ratio of the raw material to the solvent is 1: 1-1: 2.

the VIII group metal is impregnated into the carrier, then vulcanized and then impregnated with the VIB group metal, the VIII group metal in the catalyst is firstly vulcanized to form more active edges, corners and edges, the VIB group metal is loaded on the active sites to promote the interaction of the VIB group metal and the VIII group metal to form active sites with impurity poisoning resistance, so that the activity and the impurity poisoning resistance of the catalyst are improved, meanwhile, the VIB group metal content in the catalyst is low, the cracking reaction in the hydrogenation reaction process of petroleum resin can be effectively weakened, and the reduction of the softening point of the petroleum resin is prevented.

Detailed Description

The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention. The composition of the catalyst provided by the invention can be characterized by combining inductively coupled plasma ICP and XPS energy spectrums, and the total content of VIB group metals and the total content of the VIB group metals in the catalyst are firstly characterized by ICPAnd (3) quantitatively characterizing the content of metal elements with different valence states in the catalyst by an XPS spectrometer. The interaction species of the VIB group metal and the VIII group metal of the catalyst provided by the invention containsThe weight mol accounts for the total content of the VIB group metal and is expressed by the content of Mo-Co-S, Mo-Ni-S, W-Co-S, W-Ni-S. And (3) measuring the infrared spectrum of the CO adsorbed by the catalyst by adopting a Nicolet 6700 Fourier transform infrared spectrometer, then performing peak-splitting fitting on the spectrogram, and calculating according to the peak area to obtain the Mo-Co-S, Mo-Ni-S, W-Co-S, W-Ni-S content.

Analysis and detection instrument and execution standard: color values: the United states Hunter LabColour Quest EX colorimetric analyzer, implements the standard ASTM E313. Bromine number: mettler TOLEDO model DL58 titrator, USA, implements standard ASTM D1159-93. Softening point: a domestic SYD-2806F softening point tester, which is in accordance with the standard GB/T12007.6-1989. Chlorine content: a domestic RPA-200A microcoulometric titrator, performing standard large hospital joint DIPP 81.

Example 1

Dissolving nickel acetate in deionized water to prepare a solution, wherein the NiO concentration in the solution is 0.15g/mL, soaking 100mL of the solution in 120g of alumina carrier, drying at 120 ℃, and then adopting a solution containing 2.0% of H₂Sulfurizing S hydrogen at 250 deg.C under 3.0MPa for 8 hr, and adding N₂And cooling to room temperature in the atmosphere to obtain the catalyst precursor.

Dissolving ammonium metatungstate in deionized water to prepare solution, and adding WO in the solution₃At a concentration of 0.26g/mL, 30mL of the solution was immersed in the catalyst precursor in equal volume, followed by N₂Drying at 110 ℃ for 3h and roasting at 320 ℃ for 3h under the atmosphere to obtain the catalyst C-1.

Example 2

Dissolving nickel acetate into deionized water to prepare a solution, wherein the NiO concentration in the solution is 0.15g/mL, soaking 100mL of the solution into 120g of a silica-modified alumina carrier, drying at 120 ℃, and then adopting a solution containing 2.0% of H₂Sulfurizing S hydrogen at 300 deg.C under 3.5MPa for 8 hr, and adding N₂And cooling to room temperature in the atmosphere to obtain the catalyst precursor.

Dissolving ammonium molybdate into deionized water to prepare solution, wherein MoO is contained in the solution₃The concentration was 0.3g/mL, and 30mL of the solution was immersed in the catalyst in the same volumeIn a precursor of the reagent, then in N₂Drying at 110 ℃ for 3h and roasting at 300 ℃ for 3h under the atmosphere to obtain the catalyst C-2.

Example 3

Dissolving cobalt nitrate into deionized water to prepare a solution, wherein the CoO concentration in the solution is 0.4g/mL, soaking 100mL of the solution into 150g of P-modified alumina carrier, drying at 120 ℃, and then adopting a solution containing 2.0% of H₂Sulfurizing S hydrogen at 250 deg.C under 3.0MPa for 8 hr, and adding N₂And cooling to room temperature in the atmosphere to obtain the catalyst precursor.

Dissolving ammonium metatungstate in deionized water to prepare solution, and adding WO in the solution₃At a concentration of 0.26g/mL, 45mL of the solution was immersed in the catalyst precursor in equal volume, followed by N₂Drying at 110 ℃ for 3h and roasting at 320 ℃ for 3h under the atmosphere to obtain the catalyst C-3.

Example 4

Dissolving nickel nitrate and cobalt nitrate into deionized water to prepare a solution, wherein the concentration of NiO in the solution is 0.1g/mL, the concentration of CoO in the solution is 0.12g/mL, soaking 100mL of the solution and the like into 120g of alumina carrier, drying at 120 ℃, and then adopting a solution containing 2.0% of H₂Sulfurizing S hydrogen at 350 deg.C under 3.0MPa for 8 hr, and adding N₂And cooling to room temperature in the atmosphere to obtain the catalyst precursor.

Dissolving ammonium metatungstate in deionized water to prepare solution, and adding WO in the solution₃At a concentration of 0.26g/mL, 30mL of the solution was immersed in the catalyst precursor in equal volume, followed by N₂Drying at 110 ℃ for 3h and roasting at 320 ℃ for 3h under the atmosphere to obtain the catalyst C-4.

Example 5

Dissolving nickel acetate in deionized water to prepare a solution, wherein the concentration of NiO in the solution is 0.25g/mL, soaking 100mL of the solution in an equal volume into 130g of alumina carrier, drying at 120 ℃, and then adopting a solution containing 2.0% H₂Sulfurizing S hydrogen at 250 deg.C under 3.0MPa for 8 hr, and adding N₂Cooling to room temperature in atmosphere to obtainTo the catalyst precursor.

Dissolving ammonium metatungstate and ammonium molybdate into deionized water to prepare solution, and adding WO into the solution₃The concentration is 0.2g/mL, MoO₃At a concentration of 0.12g/mL, 30mL of the solution was immersed in the catalyst precursor in equal volume, followed by N₂Drying at 110 ℃ for 3h and roasting at 320 ℃ for 3h under the atmosphere to obtain the catalyst C-5.

Comparative example 1

Dissolving nickel acetate into deionized water to prepare a solution, wherein the concentration of NiO in the solution is 0.15g/mL, soaking 100mL of the solution into 120g of an alumina carrier, and then drying at 120 ℃ to obtain a catalyst precursor.

Dissolving ammonium metatungstate in deionized water to prepare solution, and adding WO in the solution₃30mL of the impregnation solution was immersed in the catalyst precursor at a concentration of 0.26g/mL, followed by N₂Drying at 110 ℃ for 3h in the atmosphere, and roasting at 320 ℃ for 3h to obtain the catalyst DC-1.

Comparative example 2

Dissolving nickel acetate and ammonium metatungstate into deionized water to prepare a solution, wherein the concentration of NiO in the solution is 0.15g/mL, and WO₃The catalyst DC-2 was obtained by impregnating 100mL of the solution into 120g of an alumina carrier at a concentration of 0.078g/mL, drying at 120 ℃ and calcining at 320 ℃ for 3 hours.

Comparative example 3

120g of alumina carrier is put into 90ml of deionized water containing 0.006g/ml of palladium chloride, after the completion of impregnation, 120ml of hydrazine hydrate with the concentration of 40 percent is used for reduction for 2 hours, the obtained product is washed by the deionized water until no chloride ion exists, and then the obtained product is dried for 3 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 700 ℃ to obtain the catalyst DC-3. Wherein the palladium content is 0.26% of the total weight of the catalyst.

TABLE 1 catalyst active Metal composition

Example 6

This example demonstrates the performance of the catalyst provided by the present invention for hydrogenation reactions on petroleum resins.

The petroleum resin evaluated was a commercially available mixed carbon five petroleum resin, which was dissolved in a cyclohexane solvent to form a 40wt% raw material solution having a chlorine content of 986ppm and a sulfur content of 42.3 ppm.

The hydrogenation performance of the catalysts C-1 to C-5 and the comparative examples DC-1 to DC-3 were evaluated by using a 200mL fixed bed petroleum resin hydrogenation apparatus.

Presulfiding conditions for catalysts C-1 to C-5, comparative examples DC-1 to DC-2 catalysts: using a catalyst containing 3wt% of CS₂The space velocity of the aviation kerosene is 1.0h^-1Presulfurizing the catalyst at an operating pressure of 5.0MPa with a hydrogen-oil volume ratio of 500: 1.

The prevulcanisation process is as follows: feeding pre-vulcanized oil at 120 ℃, feeding oil for 2h, vulcanizing at constant temperature for 2h, heating to 150 ℃ at a speed of 15 ℃/h, vulcanizing at constant temperature for 4h, heating to 300 ℃ at a speed of 10 ℃/h, vulcanizing at constant temperature for 6h, naturally cooling to 150 ℃, and finishing the pre-vulcanization.

Catalysts C-1 to C-5, comparative examples DC-1 to DC-3 the reaction conditions were evaluated as follows: the reaction temperature is 220 ℃, the operation pressure is 8.0Mpa, and the liquid raw material volume space velocity is 0.3h^-1Hydrogen volume space velocity of 200h^-1After the reaction is carried out for 200 hours, the reaction mixture is firstly subjected to alkali washing and water washing, and then the solvent and byproducts are removed by a falling film evaporator to obtain a solid resin product, and the solid resin product is analyzed and detected, wherein the evaluation result is shown in table 2.

TABLE 2 Properties and evaluation results of the catalyst after vulcanization

The evaluation results in table 2 can show that the petroleum resin hydrogenation catalyst of the present invention achieves higher hydrogenation activity, impurity poisoning resistance and stability when used in the hydrogenation reaction of petroleum resin.