阅读说明：本技术 C5石油树脂加氢催化剂及其制备方法 (C5Petroleum resin hydrogenation catalyst and preparation method thereof ) 是由 刘丽 杨成敏 姚运海 段为宇 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C-5石油树脂加氢催化剂及其制备方法。以所述催化剂的总重量为基准,包括Mo和/或W的硫化物为3wt%～8wt%,还原态Co和/或Ni为13wt%～20wt%,多孔性无机耐熔氧化物为72%～84%。C-5石油树脂加氢催化剂的制备方法,包括如下内容：(l)用Mo和/或W活性金属浸渍液浸渍多孔性无机耐熔氧化物,然后干燥处理,然后干燥后的物料进行硫化处理,得到催化剂前体；(2)用Co和/或Ni活性金属浸渍液浸渍到步骤(1)所得的催化剂前体,然后在惰性气氛下进行干燥和焙烧,然后进行还原处理,得到C-5石油树脂加氢催化剂。本发明催化剂应用石油树脂加氢过程具有高的加氢活性和高的抗硫、抗氯等杂质中毒的能力,具有很高的稳定性。(The invention discloses a C 5 A petroleum resin hydrogenation catalyst and a preparation method thereof. Based on the total weight of the catalyst, the catalyst comprises 3-8 wt% of Mo and/or W sulfide, 13-20 wt% of reduced Co and/or Ni and 72-84 wt% of porous inorganic refractory oxide. C 5 The preparation method of the petroleum resin hydrogenation catalyst comprises the following steps: (l)) Soaking porous inorganic refractory oxide in Mo and/or W active metal soaking liquid, drying, and sulfurizing to obtain catalyst precursor; (2) dipping the catalyst precursor obtained in the step (1) in a Co and/or Ni active metal dipping solution, drying and roasting the catalyst precursor in an inert atmosphere, and then carrying out reduction treatment to obtain C 5 A petroleum resin hydrogenation catalyst. The catalyst has high hydrogenation activity, high sulfur resistance, high chlorine resistance and other impurity poisoning resistance in the petroleum resin hydrogenation process, and high stability.)

1. C₅The petroleum resin hydrogenation catalyst is characterized in that: based on the total weight of the catalyst, the catalyst comprises 3-8 wt% of Mo and/or W sulfide, 13-20 wt% of reduced Co and/or Ni and 72-84 wt% of porous inorganic refractory oxide.

2. The catalyst of claim 1, wherein: the porous inorganic refractory oxide is selected from one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, silicon magnesium oxide, aluminum magnesium oxide or the oxide modified by modified elements; further preferred is alumina or modified alumina.

3. The catalyst of claim 2, wherein: the modified element is B, P, F, and the weight percentage of the modified element is 0.5wt% -10 wt% based on the weight of the modified oxide.

4. C₅The preparation method of the petroleum resin hydrogenation catalyst is characterized by comprising the following steps: (l) Soaking porous inorganic refractory oxide in Mo and/or W active metal soaking liquid, drying, and sulfurizing to obtain catalyst precursor; (2) dipping the catalyst precursor obtained in the step (1) in a Co and/or Ni active metal dipping solution, drying and roasting the catalyst precursor in an inert atmosphere, and then carrying out reduction treatment to obtain C₅A petroleum resin hydrogenation catalyst.

5. The method of claim 4, wherein: the mass concentration of the Mo and/or W active metal impregnation liquid in the step (1) is 0.01-1.0 g/mL calculated by oxides.

6. The method of claim 4, 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.

7. The method of claim 4, 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 3.2-6.4 MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

8. The method of claim 4, wherein: the mass concentration of Co and/or Ni in the Co and/or Ni active metal impregnation liquid in the step (2) is 0.1-1.0 g/mL in terms of oxide, and an equal-volume impregnation mode can be adopted.

9. The method of claim 4, wherein: 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.

10. The method of claim 4, wherein: the reduction treatment conditions in the step (2) are as follows: a hydrogen reduction method is adopted, the reduction pressure is 1.5-3.5 MPa, the reduction temperature is 150-300 ℃, the reduction time is 3-24 hours, and the hydrogen flow is 100-500 mL/min.

11. C according to claim 1₅The application of the petroleum resin hydrogenation catalyst in the hydrogenation reaction of petroleum resin.

12. Use according to claim 11, characterized in that: the hydrogenation 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 1: 3-1: 4; the solvent is cyclohexane, cyclopentane, toluene or xyleneOne or more, the weight ratio of the raw materials to the solvent is 1: 1-1: 2.

Technical Field

The invention relates to the technical field of oil product hydrogenation, in particular to a catalyst C₅A 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.

CN109482189A discloses a preparation method of a nickel-based C5 petroleum resin hydrogenation catalyst. The nickel-based hydrogenation catalyst is prepared by adopting aluminum isopropoxide and isopropanol solution as reaction base solution, zirconium and magnesium elements as additives, nickel as a catalytic active component and an organic surfactant as a dispersing auxiliary agent. The catalyst adopts nickel as an active component, but the nickel is easy to aggregate and grow up, so that the number of active centers is reduced, and the activity of the catalyst is reduced.

EP82716 discloses a supported nickel sulfide-tungsten catalyst containing 2-10 wt% of Ni and 10-25 wt% of W. The catalyst has strong sulfur resistance, but tungsten oxide is harder to be vulcanized than nickel oxide in the oxidation state of the active metal in the vulcanization process, and the vulcanization state tungsten is easy to wrap the vulcanization state nickel, so that the number of active centers is reduced, the activity of the catalyst is reduced, and the reaction temperature and the reaction pressure are higher.

CN 109395739A discloses a petroleum resin hydrogenation catalyst and a preparation method thereof. The catalyst comprises a carrier and an active component, wherein the carrier is an alumina-silica composite carrier, and the active component comprises nickel oxide and tungsten oxide. Before the hydrogenation reaction of petroleum resin, the active metal exists in oxidation state, and the nickel oxide is easier to reduce than tungsten oxide, so that the interaction between the metal nickel and tungsten is weakened, and the activity of the catalyst is reduced.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a C₅A petroleum resin hydrogenation catalyst and a preparation method thereof. The catalyst of the present invention has high hydrogenation activity, high sulfur, chlorine and other impurity poisoning resistance and high stability. The catalyst of the invention can be applied to the hydrogenation process of petroleum resin, and is particularly suitable for C₅Petroleum resin hydrogenation process.

C of the invention₅The petroleum resin hydrogenation catalyst comprises 3-8 wt% of Mo and/or W sulfide, 13-20 wt% of reduced Co and/or Ni and 72-84 wt% of porous inorganic refractory oxide, wherein the total weight of the catalyst is taken as a reference;

the porous inorganic refractory oxide is selected from one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, silicon magnesium oxide, aluminum magnesium oxide or the oxide modified by modified elements, and aluminum oxide or modified aluminum oxide is further preferable; the modified element is B, P, F, and the weight percentage of the modified element is 0.5wt% -10 wt% based on the weight of the modified oxide.

The invention provides a compound C₅The preparation method of the petroleum resin hydrogenation catalyst comprises the following steps:

(l) Soaking porous inorganic refractory oxide in Mo and/or W active metal soaking liquid, drying, and sulfurizing to obtain catalyst precursor;

(2) dipping the catalyst precursor obtained in the step (1) in a Co and/or Ni active metal dipping solution, drying and roasting the catalyst precursor in an inert atmosphere, and then carrying out reduction treatment to obtain C₅A petroleum resin hydrogenation catalyst.

In the method of the present invention, the preparation method of the Mo and/or W active metal impregnation solution in the step (1) is well known to those skilled in the art, for example, a phosphate or ammonium salt solution is generally adopted, and the mass concentration of Mo and/or W oxide in the impregnation solution is 0.01g/mL to 1.0g/mL, and an equal volume impregnation method can be adopted.

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 3.2-6.4 MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

In the method of the present invention, the preparation method of the Co and/or Ni active metal impregnation solution in the step (2) is well known to those skilled in the art, for example, nitrate, acetate, sulfate solution, etc. are generally adopted, and the mass concentration of Co and/or Ni oxide in the impregnation solution is 0.1g/mL to 1.0g/mL, and an equal volume impregnation manner can be adopted.

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

In the method of the present invention, the reduction treatment conditions in step (2) are: and (2) adopting a hydrogen reduction method, wherein the reduction pressure is 1.5-3.5 MPa, the reduction temperature is 150-300 ℃, the reduction time is 3-24 hours, the hydrogen flow is 100-500 mL/min, and the catalyst after reduction treatment is stored in nitrogen or inert gas.

C of the invention₅The petroleum resin hydrogenation catalyst is applied to the petroleum resin hydrogenation reaction, 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 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.

because the catalyst exists in an oxidation state before vulcanization or reduction, Mo and/or W is difficult to vulcanize or reduce, and Co and/or Ni is easy to vulcanize or reduce, the phenomenon that the vulcanized or reduced Co and/or Ni is wrapped by the vulcanized or reduced Mo and/or W is easily caused in the vulcanization or reduction process of the catalyst before formal use, so that the Co and/or Ni cannot fully exert the hydrogenation activity, and the activity of the catalyst is reduced. The method comprises the steps of firstly impregnating VIB group metal on a carrier by means of stepwise impregnation, vulcanization and reduction of different active metals, then carrying out presulfurization, then impregnating Co and/or Ni oxides on Mo and/or W sulfides, and then reducing the Co and/or Ni oxides to obtain the petroleum resin hydrogenation catalyst. The above process not only enables the components to be fully vulcanized and reduced, avoids the occurrence of a wrapping phenomenon, but also enables the reduced Co and/or Ni to cover the surface of the vulcanized Mo and/or W, promotes the interaction between the vulcanized Mo and/or W and the reduced Co and/or Ni, fully exerts the hydrogenation activity of the reduced Co and/or Ni and the hydrogenation desulfurization and dechlorination activity of Mo and/or W sulfides, and further improves the overall activity and stability of the catalyst.

Detailed Description

The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention. The catalyst composition provided by the invention can be characterized by combining inductively coupled plasma ICP and XPS energy spectrums, wherein the total content of various metals in the catalyst is firstly characterized by ICP, and then the content of metal elements with different valence states in the catalyst is quantitatively characterized by an XPS spectrometer.

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 ammonium molybdate in deionized water to prepare MoO₃Soaking 100mL of the solution in 0.11g/mL of alumina carrier, drying at 200 deg.C for 3 hr, and adding 2.0% H₂Sulfurizing S hydrogen at 320 deg.C under 5.0MPa for 8 hr, and adding N₂And cooling to room temperature in the atmosphere to obtain the catalyst precursor.

Dissolving cobalt nitrate in deionized water to prepare an impregnation liquid with a CoO content of 0.64g/mL, impregnating 60mL of the impregnation liquid into a catalyst precursor, and then carrying out N-phase oxidation on the catalyst precursor₂Drying at 110 deg.C for 3H, calcining at 250 deg.C for 3H, and adding 120mL/min H₂And reducing the mixture for 5 hours at the temperature of 250 ℃ and under the pressure of 2.0MPa, and storing the mixture in nitrogen to obtain the catalyst C-1.

Example 2

Dissolving ammonium molybdate in deionized water to prepare MoO₃A solution having a concentration of 0.11g/mL, 100mL of the solution was impregnated into 150g of a silica-modified alumina support, dried at 150 ℃ for 3 hours, and then used with a solution containing 3.0% H₂Sulfurizing S hydrogen at 320 deg.C under 5.0MPa for 8 hr, and adding N₂Cooling to room temperature in the atmosphere to obtain a catalyst precursor。

Dissolving nickel nitrate in deionized water to prepare an impregnation solution with NiO content of 0.64g/mL, impregnating 60mL of the impregnation solution into a catalyst precursor, and then carrying out N-phase oxidation on the catalyst precursor₂Drying at 110 deg.C for 3H, calcining at 250 deg.C for 3H, and adding 120mL/min H₂And reducing the mixture for 5 hours at the temperature of 200 ℃ and under the pressure of 3.0MPa, and storing the mixture in nitrogen to obtain the catalyst C-2.

Example 3

Dissolving ammonium metatungstate in deionized water to prepare WO₃0.13g/mL solution, 100mL solution was impregnated into 150g of silica-modified alumina support, dried at 150 ℃ for 3 hours, and then a solution containing 3.0% H was used₂Sulfurizing S hydrogen at 320 deg.C under 5.0MPa for 8 hr, and adding N₂And cooling to room temperature in the atmosphere to obtain the catalyst precursor.

Dissolving nickel nitrate in deionized water to prepare an impregnation solution with NiO content of 0.64g/mL, impregnating 60mL of the impregnation solution into a catalyst precursor, and then carrying out N-phase oxidation on the catalyst precursor₂Drying at 110 deg.C for 3H, calcining at 250 deg.C for 3H, and adding 120mL/min H₂And reducing the mixture for 5 hours at the temperature of 250 ℃ and under the pressure of 2.0MPa, and storing the mixture in nitrogen to obtain the catalyst C-3.

Example 4

Dissolving ammonium metatungstate in deionized water to prepare WO₃0.13g/mL solution, 100mL solution was impregnated into 150g of silica-modified alumina support, dried at 150 ℃ for 3 hours, and then 3wt% CS was used₂Carrying out vulcanization treatment on the aviation kerosene at the airspeed of 1.0h^-1Sulfurizing at 320 deg.C and hydrogen-oil volume ratio of 500:1 under 5.0MPa for 8 hr, and adding N₂And cooling to room temperature in the atmosphere to obtain the catalyst precursor.

Dissolving nickel nitrate and cobalt nitrate in deionized water to prepare an impregnation solution with NiO content of 0.38g/mL and CoO content of 0.25g/mL, impregnating 60mL of the impregnation solution into a catalyst precursor, and then carrying out N-phase oxidation on the catalyst precursor₂Drying at 110 deg.C for 3H, calcining at 250 deg.C for 3H, and adding 120mL/min H₂Reducing at 250 deg.C and 2.0MPa for 5 hr under nitrogenStoring in gas to obtain the catalyst C-4.

Example 5

Dissolving ammonium metatungstate and ammonium molybdate in deionized water to prepare WO₃The concentration is 0.08g/mL and MoO₃0.05g/mL of the solution, 100mL of the solution was impregnated into 150g of a silica-modified alumina support, dried at 150 ℃ for 3 hours, and then charged with 3wt% CS₂Carrying out vulcanization treatment on the aviation kerosene at the airspeed of 1.0h^-1Sulfurizing at 320 deg.C and hydrogen-oil volume ratio of 500:1 under 5.0MPa for 8 hr, and adding N₂And cooling to room temperature in the atmosphere to obtain the catalyst precursor.

Dissolving nickel nitrate in deionized water to prepare an impregnation solution with NiO content of 0.76g/mL, impregnating 60mL of the impregnation solution into a catalyst precursor, and then carrying out N-phase oxidation on the catalyst precursor₂Drying at 110 deg.C for 3H, calcining at 250 deg.C for 3H, and adding 120mL/min H₂And reducing the mixture for 5 hours at the temperature of 250 ℃ and under the pressure of 2.0MPa, and storing the mixture in nitrogen to obtain the catalyst C-5.

Comparative example 1

Dissolving ammonium molybdate and cobalt nitrate in deionized water to prepare MoO₃Soaking 100mL of solution with concentration of 0.11g/mL and CoO content of 0.38g/mL into 150g of alumina carrier, drying at 200 deg.C for 3H, calcining at 250 deg.C for 3H, and adding 120mL/min H₂And reducing the mixture for 5 hours at the temperature of 250 ℃ and under the pressure of 2.0MPa, and storing the mixture in nitrogen to obtain the catalyst DC-1.

Comparative example 2

Dissolving ammonium molybdate in deionized water to prepare MoO₃A catalyst precursor was obtained by immersing 100mL of the solution in 150g of an alumina carrier in a 0.11g/mL solution and drying at 200 ℃ for 3 hours.

Dissolving cobalt nitrate in deionized water to prepare an impregnation liquid with a CoO content of 0.64g/mL, impregnating 60mL of the impregnation liquid into a catalyst precursor, and then carrying out N-phase oxidation on the catalyst precursor₂Drying at 110 deg.C for 3H, calcining at 250 deg.C for 3H, and adding 120mL/min H₂And reducing the mixture for 5 hours at the temperature of 250 ℃ and under the pressure of 2.0MPa, and storing the mixture in nitrogen to obtain the catalyst DC-2.

Comparative example 3

Dissolving chloroplatinic acid in deionized water to prepare an impregnation solution with the Pt content of 0.005g/mL, then drying at the temperature of 250 ℃ for 3 hours, and roasting at the temperature of 700 ℃ for 3 hours to obtain the catalyst DC-3. Wherein the platinum content accounts for 0.33 percent of the total content 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 cyclohexane solvent to form a 40% (wt) strength stock solution having a chlorine content of 3752ppm and a sulfur content of 52.6 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.

The evaluation reaction conditions were: the reaction temperature is 200 ℃, the operation pressure is 5.0MPa, and the liquid volume space velocity is 0.3h^-1Hydrogen volume space velocity of 250h^-1After the reaction is carried out for 300 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 evaluation results of catalysts

The evaluation results in Table 2 can show that the petroleum resin hydrogenation catalyst of the invention is used in the hydrogenation reaction of petroleum resin, and has the reaction temperature of 200 ℃, the operation pressure of 5.0MPa and the liquid space velocity of 0.3h^-1Space velocity of hydrogen gas of 250h^-1Under the process conditions of (3), the hydrogenation activity, the impurity poisoning resistance and the stability are higher.