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    • 专利摘要:
    A palladium / carbon catalyst containing sulfur, a method for preparing the same and a method for preparing p-phenylenediaminamine anti-oxidant A palladium (Pd) / sulfur-containing carbon catalyst, a method for preparing them and a method for using the catalyst for the catalyst are provided. prepare p-phenylenediamine rubber antioxidant (PPD). The method for preparing the sulfur-containing Pd / carbon catalyst comprises: loading Pd on activated carbon to obtain a Pd / carbon catalyst; then, prepare a paste by mixing the Pd / carbon catalyst with a solvent; then, add a sulfide to the paste, stir at a predetermined temperature; finally, filter, and acquire the sulfur-containing Pd / carbon catalyst. The application of sulfur-containing Pd / carbon catalyst in the preparation of the PPD rubber antioxidant not only improves the performance of the PPD rubber antioxidant and inhibits a material from being reduced to a corresponding alcohol, but also improves selectivity.
    公开号:BR112014006933B1
    申请号:R112014006933-6
    申请日:2012-09-24
    公开日:2021-03-09
    发明作者:Xiaonian Li；Qunfeng Zhang；Xinmin Chen；Feng Feng；Lei Ma；Chunshan Lu；Chunsheng Li
    申请人:Jiangsu Sinorgchem Technology Co., Ltd；
    IPC主号:
    专利说明:

    Technical field of the invention
    [001] The present invention relates to the field of p-phenylenediamine (PPD) antioxidants, and in particular to a sulfur-containing palladium (Pd) / activated carbon catalyst, a method for preparing the same and a method for preparing antioxidants PPD. Background of the invention
    [002] PPD antioxidants are widely used due to their favorable protective performance, and an important method of industrial synthesis of PPD antioxidants is reducing alkylation, which is a synthesis method using 4-aminodiphenylamine (4-ADPA) (based on room temperature ) and an aliphatic ketone as raw materials. For example, rubber antioxidant 4020, also known as antioxidant DMBPPD, chemical name N- (1,3-dimethylbutyl) -N'-phenyl-para-phenylenediamine (6PPD), plays an important role in aspects including ozone resistance, resistance oxidation, thermal resistance and crack resistance, etc. and it has been widely used as the popularity of meridian tires arises. The rubber antioxidant 4020 can be prepared by dehydration by hydrogenation of raw materials N-phenyl-p-phenylene diamine (base at room temperature) and methylisobutyl ketone (MIBK) in the presence of a catalyst according to the following reaction equation:

    [003] Reductive alkylation by hydrogenation can also be a two-step process consisting of step 1: Base at room temperature and MIBK react by condensation by dehydration to form an imine, and step 2: the generated imine is reduced by hydrogen at 4020, according to the following reaction equations:

    [004] In the reaction, step 1 can be carried out in the presence of a protonic acid catalyst or be carried out spontaneously, without a catalyst, and step 2 can be carried out in the presence of a hydrogenation catalyst with relatively high selectivity.
    [005] In hydrogenation-reducing alkylation to prepare PPD rubber antioxidant, the main side reactions include hydrogenation of a raw material to form a corresponding alcohol, hydrogenolysis of raw materials or products, hydrogenation of a benzene ring, and tar generated by overheating, etc. The key to synthesizing a PPD rubber antioxidant with good quality and low cost is the use of a catalyst with good activity and selectivity, and they can be recycled and reused.
    [006] Currently, catalysts for preparing PPD rubber antioxidants in the industry include copper-based catalysts and platinum-carbon catalysts. Patent No. 200610161327.2 describes a method for preparing a Cu-Zn / Al2O3 catalyst to prepare 4020 by reducing alkylation. The copper-based catalyst is relatively inexpensive, but is unsatisfactory in selectivity. Because a large amount of MIBK is hydrogenated and reduced to a corresponding alcohol, methyl isobutyl alcohol (MIBA), and the percentage of MIBA at the end of the reaction can reach between 9.3% to 97.4% of the total amount of MIBK and MIBA. As a result, raw materials are wasted and the cost is increased. In addition, platinum metal in a conventional platinum-carbon catalyst is very expensive and the cost of the product will be greatly increased by the mass industrial use of the catalyst.
    [007] Pd has been commonly used as a hydrogenation catalyst and widely used in hydrogenation reduction of radicals, including a nitro group, a carbonyl group, a carbon-carbon double bond and a carbon-nitrogen double bond, etc. However, when the palladium (Pd) / activated carbon catalyst is applied to prepare 4020 by means of reducing alkylation, raw materials and products will have severe C-N bond hydrogenolysis side reactions, so that the selectivity for the product target is very low.
    [008] To date, Pd has not been used successfully as an active component in the catalyst to prepare a PPD rubber antioxidant with a high conversion rate and high selectivity, basically because it is difficult to control the hydrogenolysis side reactions the CN bond caused by the application of the Pd catalyst. Summary of the invention
    [009] To solve the problems of an existing copper-based catalyst not being satisfactory in selectivity, while a platinum-carbon catalyst is expensive, the present invention provides a sulfur-containing Pd / carbon catalyst, a method for preparing the same and an application of it.
    [0010] A method for preparing a sulfur-containing Pd / carbon catalyst of the present invention includes the following steps: - loading Pd on an activated carbon to obtain a Pd / carbon catalyst; - mixing the Pd / carbon catalyst with a solvent to obtain a paste; - add a sulphide to the paste and stir carefully at a predetermined temperature; - filter to obtain the sulfur-containing Pd / carbon catalyst.
    [0011] Preferably, in the step of adding the sulfide to the paste, the molar ratio of added sulfide to Pd loaded on the Pd / carbon catalyst is 0.1 to 10: 1. More preferably, the molar ratio of added sulfide to Pd loaded on the Pd / carbon catalyst is 0.1 to 1: 1.
    [0012] Preferably, the sulfide adopted in the preparation process can be selected from one or more of a group consisting of thiol, thioether, alkyl disulfide, thiofuran, hydrogen sulfide, ammonium sulfide, ammonium hydrosulfide, a an alkali metal sulfide and an alkali metal hydrosulfide.
    [0013] Most preferably, the sulfide is selected from one or more of a group consisting of methyl mercaptan, ethyl thiol, methyl thioether, ethyl thioether, diphenyl thioether, dimethyl disulfide, thiophuran, hydrogen sulfide, ammonium sulfide, ammonium hydrosulfide, sodium sulfide and potassium hydrosulfide. In a specific embodiment provided by the present invention, the sulfide adopted is diphenyl thioether or dimethyl disulfide.
    [0014] In the preparation method provided by the present invention, adopted solvent can be methanol, ethanol, acetone, MIBK or water.
    [0015] In the preparation method provided by the present invention, preferably, the granularity of the activated carbon adopted is 50 to 1000 meshs; the special surface area is 600 to 1800 m2 / g and the amount of Pd charge is 0.5 to 10% by weight.
    [0016] Another objective of the present invention is to provide a sulfur-containing Pd / carbon catalyst. The sulfur-containing Pd / carbon catalyst is prepared by the method described above.
    [0017] A third object of the present invention is to provide a method for preparing a PPD rubber antioxidant. The method uses 4-ADPA and an aliphatic ketone as raw materials, and the sulfur-containing Pd / carbon catalyst as a catalyst to prepare a PPD compound. Preferably, the sulfur-containing Pd / carbon catalyst is added to the reaction system in an amount such that the weight ratio of Pd loaded on the sulfur-containing Pd / carbon catalyst to 4-ADPA is 0.01 to 1% by weight .
    [0018] Preferably, the method for preparing PPD rubber antioxidant includes the following steps: use 4-ADPA and aliphatic ketone as the raw materials, add the sulfur-containing Pd / carbon catalyst directly to the reaction system while stirring , introduce a predetermined amount of hydrogen, and synthesize the rubber antioxidant PPD through liquid phase hydrogenation.
    [0019] Different from the steps above, the method for preparing the PPD rubber antioxidant of the present invention can be implemented by the following steps: using 4-ADPA and the aliphatic ketone as the raw materials and a protonic acid or activated carbon as a catalyst , perform condensation by dehydration at 120 ° C to 150 ° C while stirring to synthesize an intermediate product; add the sulfur-containing Pd / carbon catalyst to a reaction system formed by the intermediate product and a solvent, introduce a predetermined amount of hydrogen, and synthesize the PPD rubber antioxidant through liquid phase hydrogenation.
    [0020] The sulfur-containing Pd / carbon catalyst prepared by the method of preparation provided by the present invention exhibits good activity, selectivity and indiscriminate usage performance, and can be used to prepare the PPD rubber antioxidant. Applied in the preparation of the PPD rubber antioxidant, the sulfur-containing Pd / carbon catalyst not only improves the performance of the PPD rubber antioxidant and inhibits the raw materials from being reduced to corresponding alcohols, but also improves the selectivity of the reaction. Brief description of the drawings
    [0021] Fig. 1 shows a method flow diagram for preparing a sulfur-containing Pd / carbon catalyst provided by the present invention. Detailed description of the invention
    [0022] Modalities of the present invention will be described in detail below. However, the following modalities are used only for the understanding of the present invention, rather than limiting the present invention. The present invention can be implemented through a number of different methods limited and covered by the claims.
    [0023] Fig. 1 shows a method for preparing a sulfur-containing Pd / carbon catalyst provided by the present invention, including the following steps: loading Pd on an activated carbon to obtain a Pd / carbon catalyst; mixing the Pd / carbon catalyst with a solvent to obtain a paste; add a sulfide to the paste, stirring carefully at a predetermined temperature; filter to obtain the sulfur-containing Pd / carbon catalyst. Through the preparation method provided by the present invention, Pd is initially loaded onto activated carbon and then reacts with the sulfide while loaded onto the activated carbon in order to be partially passivated. As a result, the use of the catalyst reduces by-products produced during the process of preparing the PPD rubber antioxidant. It is unexpected to discover that sulfide can hardly convert the Pd metal loaded on activated carbon into palladium sulfide completely, and the sulfur is only selectively adsorbed and combined on the surfaces of the Pd metal particles and several palladium sulfides are formed. Due to the selective adsorption and various palladium sulphides, the activity of Pd loaded on activated carbon is partially passivated, therefore, the problem of the drop in target product caused selectively by serious secondary reactions of CN bond hydrogenolysis in raw materials and products has been solved. .
    [0024] The "charging Pd covers an activated carbon" step mentioned in the process of preparing the present invention belongs to the prior art, and a conventional charging method can be applied. For example, in a specific embodiment provided by the present invention, the Pd / carbon catalyst can be prepared using the following method: weigh an activated carbon used to prepare the catalyst, prepare the activated carbon in a paste at a temperature of 60 ° C at 90 ° C, slowly add an H2PdCl4 solution dropwise according to the amount of Pd charge, stir carefully and mix evenly, after immersion from 0.5 to 5 h, adjust the pH value of the solution to 7.1 to 9, reduce the temperature to room temperature, filter, wash a filter cake to be neutral with deionized water, then prepare the filter cake in a paste at 20 ° C and 90 ° C, add drop drop a liquid phase reducing agent to allow a reduction reaction, then filter to obtain the Pd / carbon catalyst. The reducing agent in the reduction step can be formaldehyde, methanol, formic acid or an alkali metal salt of formic acid or hydrazine hydrate. Preferably, in the reduction reaction process, the molar ratio of the reducing agent to Pd is 2 to 200: 1, preferably 5 to 50: 1. Preferably, the temperature for the reduction reaction is 20 ° C to 100 ° C, and more preferably, about 30 ° C to 80 ° C. When the reduction is carried out under preferential conditions, the reduction effect is more evident, and most of the Pd ions charged on activated carbon can be reduced to Pd.
    [0025] It should be noted that the amount of Pd charge in the Pd / carbon catalyst prepared by the present invention is preferably controlled within 0.5 to 10% by weight, and more preferably about 1 to 5% by weight , because the amount of Pd charge affects subsequent reactions in which, if the amount of Pd charge is too low, more time is needed for the preparation of the PPD rubber antioxidant, which is not suitable for industrial production; if the amount of Pd charge is too high, the stereoselectivity of a possible product is affected. However, a sulfur-containing Pd / carbon catalyst, in addition to this range, still works well in improving the yield and selectivity of the PPD rubber antioxidant and prevents raw materials from being reduced to the corresponding alcohols.
    [0026] The amount of Pd charge can be accurately determined by the prior art. For example, a standard method for determining the amount of Pd charge on a Pd / carbon catalyst is provided in the National Standard of R.P. of China, GB / T 23518-2009.
    [0027] Preferably, the granularity of the activated carbon adopted in the present invention is 50 to 1000 mesh, preferably 80 to 500 mesh; and the special surface area is 600 to 1800 m2 / g, and preferably 1000 to 1500 m2 / g. In the ranges of granularity and special surface area, the load of Pd on activated carbon is easier, and the distribution of the loaded Pd is relatively uniform.
    [0028] After the Pd / carbon catalyst is obtained, the Pd / carbon catalyst is mixed with a solvent to form a paste. In the step, the objective is to make the Pd / carbon catalyst in the paste. Preferably, the solvent adopted here has a certain polarity in order to optimize the dispersion of the Pd / carbon catalyst. For example, the solvent used in a specific embodiment provided by the present invention can be an alcohol, a ketone or water, for example, methanol, ethanol, acetone, MIBK, isopropanol, tert-butanol, isoamyl ketone, octanone, or water. It can be seen from the applicable solvents that the solvent adopted by the preparation method of the present invention varies, and there is no strict requirement for the specific solvent. In addition, the solvent adopted is inexpensive and very suitable for industrial production.
    [0029] Furthermore, during the step of mixing the Pd / carbon catalyst with the solvent to form the slurry, preferably the volume ratio of the Pd / carbon catalyst to solvent is controlled within 1: 5 to 1000, and preferably 10 to 400: 1. If the volume of the solvent is too small, it is difficult to form the paste; if the volume of the solvent is too large, energy is wasted and there is a problem of after-treatment of the solvent.
    [0030] An essential step of the present invention is a sulfuration step and the Pd / carbon catalyst can be prepared through the step. The sulfurization step includes: after preparing the paste, add the sulfide to the slurry and stir carefully at a predetermined temperature. After this step, the sulfide and Pd loaded on the Pd / carbon catalyst react carefully so that Pd is partially passivated, and thus, the risk of Pd acting on CN bonds in raw materials or products to cause cracks in the bonds and formation of numerous by-products is less. Preferably, the molar ratio of the added sulfide to Pd loaded on the Pd / carbon catalyst is 0.1 to 10: 1, and more preferably, 0.1 to 1: 1. Within the preferred range, activated carbon has a good catalytic performance after sulfurization, and secondary hydrogenolysis reactions can be well controlled. Of course, it can be seen from a specific modality provided by the present invention that, activated carbon beyond the preferred range also has controllability over the hydrogenolysis side reactions.
    [0031] The sulfide mentioned in the present invention refers to such a sulfide: a sulfurizing agent that reacts with the metal Pd to have adsorption and coordination effects in order to reduce the catalytic activity of the metal Pd. Sulfur atoms in the sulfurizing agent must have electrons in lone pair so that the sulfurizing agent can have the coordination effect with the metal Pd. Therefore, in principle, the sulfurizing agent adopted in the present invention can be a sulfide as long as the sulfide has sulfur atoms that have electron in solitary pair. Preferably, the sulfide is selected from one or more of a group consisting of thiol, thioether, alkyl disulfide, thiofuran, hydrogen sulfide, ammonium sulfide, ammonium hydrosulfide, an alkali metal sulfide, or a hydrosulfide of an alkali metal. More preferably, the sulfide is selected from one or more of a group consisting of methyl mercaptan, ethyl thiol, methyl thioether, ethyl thioether, diphenyl thioether, dimethyl disulfide, thiophuran, hydrogen sulfide, ammonium sulfide, ammonium hydrosulfide , sodium sulfide and potassium hydrosulfide.
    [0032] In a specific embodiment provided by the present invention, when the sulfide is diphenyl thioether or dimethyl disulfide, the performance is superior to that of other substances.
    [0033] The predetermined temperature in the above reaction process can be from 20 ° C to 100 ° C, preferably from 30 ° C to 70 ° C. In addition, the time for sulfur treatment is longer than 10 minutes, preferably 2 to 5 hours. Therefore, it can be seen that the reaction provided by the present invention can be carried out within a wide temperature range, and the time for the sulfur treatment is very short, and the reaction can generally be carried out in just more than 10 minutes. Therefore, energy consumption can be greatly reduced and the cost of the product can be further reduced by the industrial application of the method.
    [0034] In a specific embodiment of the present invention, a specific sulfur treatment step process includes: after the reduced Pd / carbon catalyst is filtered, a filter cake is washed to be neutral with deionized water and dried under vacuum at 60 ° C to 110 ° C. Then, it is ready for the sulfur treatment. During the sulfur treatment step, the reduced Pd / carbon catalyst and solvent are first prepared in a paste at 20 ° C to 100 ° C and then the sulfide is added in a molar ratio of Pd to sulfide of 1: 0.1 to 10, and the stirring time is longer than 10 minutes. Then, the sulfurization step is carried out.
    [0035] After the sulfurization step, a filtrate can be filtered directly and a filter cake is dried to prepare the sulfur-containing Pd / carbon catalyst. The filter cake can also be dried under vacuum at 30 ° C to 110 ° C to completely remove the residual solvent in the catalyst. If the solvent in the sulfurization process can be introduced in the process to make the antioxidant PPD, it is not necessary to vacuum dry the catalyst.
    [0036] The sulfur-containing Pd / carbon catalyst provided by the present invention can be applied in the method of preparing the PPD rubber antioxidant. It is known to all that the rubber antioxidant PPD can be synthesized by several methods, including reducing alkylation, phenol amine condensation, hydroxylamine reducing alkylation and quinone imine condensation used in the present, while the catalyst provided by the present invention is applicable to the reaction to prepare the antioxidant PPD by reducing alkylation, for example, the catalyst provided by the present invention can be applied in the preparation of products, including 6PPD, N-isopropyl-N'-phenyl-para-phenylene diamine (IPPD), N- ( 1,4-dimethyl-pentyl) -N'-phenyl-para-phenylene diamine (7PPD), N, N'-di (1,4-imethylpentyl) -para-phenylene diamine (77PD), N-sec-octyl- N'-phenyl-para-phenylene diamine (OPDP), N, N'-di-sec-butyl-para-phenylene diamine (44PD), N-isoamyl-N'-phenyl-para-phenylene diamine (5PPD), N , N'-di- (1,3-dimethylbutyl) - para-phenylene diamine (66PD) and 2,4,6-tri- (N-1,4-dimethyl pentyl-para-phenylene-diamine) -1,3 , 5-triazine (TMPPD).
    [0037] Reductive alkylation has one-step and two-step procedures. When the catalyst is applied in a one-step preparation process, the PPD antioxidant preparation method includes the following steps: using 4-ADPA and an aliphatic ketone as raw materials, directly adding the Pd / carbon catalyst containing sulfur to the reaction system while stirring and introducing a predetermined amount of hydrogen to synthesize the rubber antioxidant PPD through liquid phase hydrogenation.
    [0038] When the catalyst is applied in a two-step preparation process, the PPD antioxidant preparation method includes the following steps: using 4-ADPA and an aliphatic ketone as raw materials and a protonic acid or carbon activated as a catalyst, perform condensation by dehydration at 120 ° C to 150 ° C while stirring to synthesize an intermediate product; add the Pd / carbon catalyst to the reaction system formed by the intermediate product and a solvent, then introduce to synthesize the rubber antioxidant PPD through hydrogenation in liquid phase.
    [0039] In a specific embodiment provided by the present invention, the catalyst provided by the present invention is applied in the preparation of an antioxidant 4020, and a one-step procedure includes the following specific process: while stirring, use a base at room temperature ( 4-ADPA) and excess MIBK as raw materials and sulfurized Pd / activated carbon as a catalyst to synthesize the rubber antioxidant 4020 through liquid hydrogenation at 90 ° C to 240 ° C and a hydrogen pressure of 1 to 5 MPa. A two-step procedure includes the following specific process: while stirring, use a base at room temperature and excess MIBK as raw materials, a protonic acid or activated carbon as a catalyst to synthesize an imine through 120 ° dehydration condensation C to 150 ° C; subject the generated imine to hydrogenation in liquid phase at 90 ° C to 220 ° C and a hydrogen pressure of 1 to 5 MPa using MIBK as a solvent and sulfurized Pd / activated carbon as a catalyst to synthesize the rubber antioxidant 4020.
    [0040] Preferably, the molar ratio of the base at room temperature to MIBK is 1: 2 to 10, preferably 1: 2 to 6. In such molar ratios, the reaction is more profound and applicable to industrial mass production .
    [0041] Preferably, the amount of catalyst used is from 0.01 to 1% by weight of the mass of the base at room temperature in the mass of Pd, preferably from 0.02 to 0.2% by weight. In such preferred ratios, the reaction can be carried out completely, and controlling the catalyst content in the preferred range can further reduce the cost of production and preparation.
    [0042] Preferably, the temperature of the one-step process is preferably 100 ° C to 200 ° C and the hydrogen pressure is preferably 1.5 to 3 MPa.
    [0043] Preferably, the dehydration reaction temperature in the two-step process is preferably 120 ° C to 140 ° C, the hydrogenation reaction temperature is preferably 100 ° C to 200 ° C and the hydrogen pressure is preferably 1.5 to 3 MPa.
    [0044] Specific preparation methods of sulfur-containing Pd / carbon catalysts provided by the present invention and the beneficial effect caused by the application of the catalysts prepared in the PPD antioxidants will be further described through the modalities below. However, the present invention is not limited to the following embodiments. Mode 1
    [0045] Weigh 10 g of activated carbon with a granularity of 100 mesh and a special surface area of 1200 m2 / g, add the activated carbon to 100 ml of deionized water to prepare a paste at a temperature of 80 ° C, add slowly 10 ml of H2PdCl4 solution (Pd content is 0.05 g / ml) dropwise, stir for 2 hours, adjust the pH of the solution to 8 with 10% by weight of NaOH solution, reduce at room temperature, filter and wash a filter cake to be neutral with deionized water, then prepare the filter cake in a paste at 40 ° C, add dropwise a solution of 2 ml of hydrazine hydrate having a concentration of 85%, stir for 2 h, filter, wash the filter cake to be neutral with deionized water, dry the filter cake at 100 ° C in a vacuum condition, perform sulfurization for the filter cake, prepare the filter cake in a paste at 40 ° C with 100 ml of methanol, add dropwise 0.1 ml of methyl mer capture, stir for 2 h, filter, dry a filter cake at 100 ° C in a vacuum condition to obtain a sulfurized Pd-activated carbon catalyst. Mode 2
    [0046] Weigh 10 g of activated carbon with a granularity of 200 mesh and a special surface area of 1400 m2 / g, add the activated carbon to 100 ml of deionized water to prepare a paste at a temperature of 60 ° C, add slowly 6 ml of H2PdCl4 solution (Pd content is 0.05 g / ml) dropwise, shake for 3 hours, adjust the pH of the solution to 8.5 with 10% by weight of NaOH solution , reduce the temperature to room temperature, filter and wash a filter cake to be neutral with deionized water, and then prepare the filter cake in a paste at 60 ° C, add 10 ml of methanol dropwise, shake for 4 hours, filter, wash the filter cake to be neutral with deionized water, dry the filter cake at 90 ° C under vacuum, perform sulfurization of the filter cake, prepare the filter cake to a paste at 60 ° C with 150 ml of ethanol, add dropwise 0.1 ml of diphenyl thioether, shake for 4 hours, filter, dry a filter cake at 80 ° C under vacuum conditions to obtain a sulfurized Pd-activated carbon catalyst. Mode 3
    [0047] Weigh 10 g of activated carbon with a granularity of 150 mesh and a special surface area of 1400 m2 / g, add the activated carbon to 100 ml of deionized water to prepare a paste at a temperature of 60 ° C, add slowly 20 ml of H2PdCl4 solution (Pd content is 0.05 g / ml) dropwise, stir for 4 hours, adjust the pH of the solution to 9 with 10% by weight of a NaOH solution, reduce the temperature to room temperature, filter and wash a filter cake to be neutral with deionized water, and then prepare the filter cake in a paste at 60 ° C, add dropwise 35ml of formaldehyde with a concentration of 40% by weight, stir for 4 hours, filter, wash the filter cake to be neutral with deionized water, dry the filter cake at 90 ° C under vacuum, perform sulfurization for the filter cake, prepare the filter cake in a paste at 60 ° C with 200 ml of acetone, add dropwise 0.8 ml of thiofuran, stir for 4 h, filter, dry a filter cake at 90 ° C under vacuum conditions to obtain a sulfurized activated Pd-carbon catalyst. Mode 4
    [0048] Weigh 10 g of activated carbon with a granularity of 400 mesh and a special surface area of 1600 m2 / g, add the activated carbon to 100 ml of deionized water to prepare a paste at a temperature of 60 ° C, add slowly 4 ml of H2PdCl4 solution (Pd content is 0.05 g / ml) dropwise, stir for 2 hours, adjust the pH of the solution to 7.5 with 10% NaOH solution by weight , reduce the temperature to room temperature, filter and wash a filter cake to be neutral with deionized water, and then prepare the filter cake in a paste at 30 ° C, add dropwise 15 mL of formic acid with a concentration 40% by weight, stir for 4 hours, filter, wash the filter cake to be neutral with deionized water, dry the filter cake at 90 ° C under vacuum, perform sulfurization for the filter cake, prepare the cake filter in a paste at 60 ° C with 50 ml of MIBK, add dropwise 0.1 ml of dimethyl disulfide, shake hard for 4 hours, filter, dry a filter cake at 110 ° C under vacuum to obtain a sulfurized activated Pd-carbon catalyst. Mode 5
    [0049] Weigh 10 g of activated carbon with a granularity of 300 mesh and a special surface area of 1600 m2 / g, add the activated carbon to 100 ml of deionized water to prepare a paste at a temperature of 60 ° C, add slowly 10 ml of H2PdCl4 solution (Pd content is 0.05 g / ml) dropwise, stir for 2 hours, adjust the pH of the solution to 8.5 with 10% by weight NaOH solution , reduce the temperature to room temperature, filter and wash a filter cake to be neutral with deionized water, and then prepare the filter cake in a paste at 30 ° C, add dropwise 3 ml of hydrazine hydrate having a concentration of 85% by weight, stir for 4 hours, filter, wash the filter cake to be neutral with deionized water, dry the filter cake at 90 ° C under vacuum, perform sulfurization for the filter cake, prepare the filter cake in a paste at 60 ° C with 200 ml of water, slowly introduce 0.5 ml of hydrogen sulphide gaseous in the form of bubbles, stir for 4 h, filter and dry a filter cake at 100 ° C in a vacuum condition to obtain a sulfurized activated Pd-carbon catalyst. Mode 6
    [0050] Weigh 10 g of activated carbon with a granularity of 250 mesh and a special surface area of 1600 m2 / g, add the activated carbon to 100 ml of deionized water to prepare a paste at a temperature of 60 ° C, add slowly 10 ml of H2PdCl4 solution (Pd content is 0.05 g / ml) dropwise, stir for 2 hours, adjust the pH of the solution to 8.5 with 10% by weight NaOH solution , reduce the temperature to room temperature, filter and wash a filter cake to be neutral with deionized water, and then prepare the filter cake in a paste at 30 ° C, add dropwise 3 ml of hydrazine hydrate having a concentration of 85% by weight, stir for 4 hours, filter, wash the filter cake to be neutral with deionized water, dry the filter cake at 90 ° C under vacuum, perform sulfurization for the filter cake, prepare the filter cake in a paste at 60 ° C with 200 ml of water, add dropwise 7 ml of a sulfide solution sodium (1.1 g / cm3) having a concentration of 10% by weight, stir for 4 hours, filter and dry a filter cake at 100 ° C in a vacuum condition to obtain an activated Pd-carbon catalyst sulfurized. Modes 7 to 13
    [0051] The preparation methods of modalities 7 to 13 are the same as the preparation method in modality 1, except that the activated carbon applied, the amount of Pd charge, the sulfide, the molar ratio of sulfide to Pd and the solvent adopted in the paste were different. The conditions are recorded in detail in Table 1 and the preparation processes will not be repeated here.
    [0052] Modes 14 and 26 are modalities for the application of Pd catalysts prepared by the above preparation methods in catalytic synthesis: Modality 14
    [0053] Add 0.74 g of Pd catalyst prepared in modality 1, 73.6 g of base at room temperature and 200 ml of MIBK to a 500 ml high pressure stainless steel reaction boiler, close the reaction, replace the air inside the reaction boiler with nitrogen three times and then with hydrogen three times, increase the temperature to 140 ° C, where the hydrogen pressure was 2 MPa, start stirring at 900 r / min, react for 4 hours, end the reaction, withdraw the reaction solution after the temperature is reduced to room temperature, filter to remove the catalyst, analyze a filtrate with gas chromatography, in which the results showed that the rate of conversion of the base at room temperature was 99.5%, the selectivity of 4020 was 99.5% and the selectivity of MIBK was 99.8%. Mode 15
    [0054] Add 0.55 g of Pd catalyst prepared in mode 2, 55.2 g of base at room temperature and 187 ml of MIBK to a 500 ml high pressure stainless steel reaction boiler, close the reaction, replace the air inside the reaction boiler with nitrogen three times and then with hydrogen three times, increase the temperature to 160 ° C, where the hydrogen pressure was 3 MPa, start stirring at 900 r / min, react for 5 hours, end the reaction, withdraw the reaction solution after the temperature is reduced to room temperature, filter to remove the catalyst, analyze a filtrate with gas chromatography, where the results showed that the conversion rate from the base the room temperature was 99.8%, the selectivity of 4020 was 98.7% and the selectivity of MIBK was 99.7%. Mode 16
    [0055] Add 0.74 g of Pd catalyst prepared in modality 3, 73.6 g of base at room temperature and 150 ml of MIBK to a 500 ml high pressure stainless steel reaction boiler, close the boiler of reaction, replace the air inside the reaction boiler with nitrogen three times and then with hydrogen three times, increase the temperature to 100 ° C, where the hydrogen pressure was 3 MPa, start stirring at 900 r / min, react for 3 hours, end the reaction, withdraw the reaction solution after the temperature is reduced to room temperature, filter to remove the catalyst, analyze a filtrate with gas chromatography, in which the results showed that the rate of conversion of the base at room temperature was 99.3%, the selectivity of 4020 was 99.5% and the selectivity of MIBK was 99.9%. Mode 17
    [0056] Add 0.55 g of Pd catalyst prepared in modality 4, 55.2 g of base at room temperature and 225 ml of MIBK to a 500 ml high pressure stainless steel reaction boiler, close the reaction, replace the air inside the reaction boiler with nitrogen three times and then with hydrogen three times, increase the temperature to 160 ° C, where the hydrogen pressure was 1 MPa, start stirring at 900 r / min, react for 6 hours, end the reaction, withdraw the reaction solution after the temperature is reduced to room temperature, filter to remove the catalyst, analyze a filtrate with gas chromatography, in which the results showed that the rate of conversion of the base at room temperature was 99.4%, the selectivity of 4020 was 99.4% and the selectivity of MIBK was 99.6%. Mode 18
    [0057] Add 1.5 g of Pd catalyst prepared in modality 5, 55.2 g of base at room temperature and 225 ml of MIBK to a 500 ml high pressure stainless steel reaction boiler, close the reaction, replace the air inside the reaction boiler with nitrogen three times and then with hydrogen three times, increase the temperature to 220 ° C, where the hydrogen pressure was 2.5 MPa, start stirring at 900 r / min, react for 4 hours, end the reaction, withdraw the reaction solution after the temperature is reduced to room temperature, filter to remove the catalyst, analyze a filtrate with gas chromatography, in which the results showed that the conversion rate of the base at room temperature was 98.9%, the selectivity of 4020 was 99.5% and the selectivity of MIBK was 99.2%. Mode 19
    [0058] Add 55.2 g of base at room temperature, 225 ml of MIBK and 2 g of activated carbon to a 500 ml round bottom flask with a water separator, increase the reaction temperature to 130] C and carry out condensation by dehydration for 4 h while stirring, add an imine obtained by condensation reaction, 150 mL of MIBK and 0.55 g of Pd catalyst prepared in embodiment 6 to a 500 high pressure stainless steel reaction boiler ml, close the reaction boiler, replace the air inside the reaction boiler with nitrogen three times and then with hydrogen three times, increase the temperature to 200 ° C, where the hydrogen pressure was 2 MPa, start stirring at 900 r / min, react for 4 hours, terminate the reaction, withdraw the reaction solution after the temperature has been reduced to room temperature, filter to remove the catalyst, analyze a filtrate with gas chromatography, in which the results show that the rate of Conversion of the base at room temperature was 99.0%, the selectivity of 4020 was 99.6% and the selectivity of MIBK was 99.1%. Modes 20 to 26
    [0059] The specific operating processes in modalities 20 to 26 are the same as those in modalities 14 to 19, except that the catalysts adopted are different and the reaction processes can be one-step procedures or two-step procedures. The specific conditions are as shown in Table 2, and the operating processes will not be repeated here. Mode 27 (Preparation of IPPD)
    [0060] Add 0.74 g of Pd catalyst prepared in mode 1, 92 g of base at room temperature and 51 ml of acetone to a 500 ml high pressure stainless steel reaction boiler, close the reaction boiler, replace the air inside the reaction boiler with nitrogen three times and then with hydrogen three times, increase the temperature to 150 ° C, where the hydrogen pressure was 3.0 MPa, start stirring at 900 r / min , react for 4 hours, finish the reaction, remove the reaction solution after the temperature is reduced to room temperature, filter to remove the catalyst, analyze a filtrate with gas chromatography, in which the results showed that the conversion rate of the base the ambient temperature was 99.5%, the selectivity of IPPD was 99.6% and the selectivity of acetone was 99.8%.
    [0061] Comparative example 1 and comparative example 2 are examples of applying unsulfurized Pd / carbon catalysts to catalyze the 4020 synthesis. Comparative example 1
    [0062] Add 1.5 g of unsulfurized Pd / carbon catalyst with a 5% load quantity, 55.2 g of base at room temperature and 225 ml of MIBK to a high pressure stainless steel reaction boiler 500 ml, close the reaction boiler, replace the air inside the reaction boiler with nitrogen three times and then with hydrogen three times, increase the temperature to 160 ° C, where the hydrogen pressure was 2.5 MPa, start stirring at 900ar / min, react for 4 h, end the reaction, withdraw the reaction solution after the temperature is reduced to room temperature, filter to remove the catalyst, analyze a filtrate by gas chromatography, in that the results showed that the conversion rate of the base at room temperature was 99.4%, the selectivity of 4020 was 81.6% and the selectivity of MIBK was 99.1%. Comparative Example 2
    [0063] Add 55.2 g of base at room temperature, 225 ml of MIBK and 2 g of activated carbon to a 500 ml round bottom flask with a water separator, increase the reaction temperature to 130 ° C and carry out condensation by dehydration for 4 h while stirring, add an imine obtained by condensation reaction, 150 ml of MIBK and 0.55 g of unsulfurized Pd / carbon catalyst with a charge value of 3% to a reaction boiler 500 ml high pressure stainless steel, close the reaction boiler, replace the air inside the reaction boiler with nitrogen three times and then with hydrogen three times, increase the temperature to 180 ° C, in that the hydrogen pressure was 2 MPa, start stirring at 900 r / min, react for 4 hours, end the reaction, withdraw the reaction solution after the temperature is reduced to room temperature, filter to remove the catalyst, analyze a filtered with gas chromatography, where the results are showed that the conversion rate of the base at room temperature was 99.8%, the selectivity of 4020 was 75.2% and the selectivity of MIBK was 99.2%. Table 1 - sulfurized Pd-activated carbon catalysts supplied by modalities 1 to 13

    Table 2 - influence of catalysts provided by the present invention and comparative examples in reactions


    [0064] Compared with the prior art, the present invention has the following advantages: 1) high activity and high selectivity, the present invention applies a sulfurized Pd / carbon catalyst for the synthesis of a PPD rubber antioxidant, for example, a 4020 rubber antioxidant reaction, exhibiting extremely high activity and selectivity, with a base conversion rate at room temperature as high as 99.8%, a 4020 selectivity as high as 99.5% and a more selectable MIBK high than 99.5%; 2) low cost, the main component of a catalyst used in the present invention is Pd and the amount of Pd charge is similar to that of platinum in a platinum / carbon catalyst, therefore, the sulfur-containing Pd / carbon catalyst, with greater economic benefit, it is cheaper than the traditional platinum / carbon catalyst.
    权利要求:
    Claims (12)
    [0001]
    1. Method for preparing a palladium (Pd) / carbon catalyst containing sulfur characterized by comprising the following steps: loading Pd on an activated carbon to obtain a Pd / carbon catalyst; mixing the Pd / carbon catalyst with a solvent to obtain a paste; add a sulfide to the paste and stir; filter to obtain the sulfur-containing Pd / carbon catalyst; the predetermined temperature being from 20 ° C to 100 ° C.
    [0002]
    2. Method according to claim 1, characterized by the fact that in the step of adding the sulfide to the paste, the molar ratio of the added sulfide to Pd loaded on the Pd / carbon catalyst is 0.1 to 10: 1.
    [0003]
    Method according to claim 2, characterized by the fact that the molar ratio of the added sulfide to Pd charged on the Pd / carbon catalyst is 0.1 to 1: 1.
    [0004]
    Method according to any one of claims 1 to 3, characterized in that the sulfide is selected from one or more in a group consisting of thiol, thioether, alkyl disulfide, thiophuran, hydrogen sulfide, ammonium sulfide, ammonium hydrosulfide, an alkali metal sulphide and an alkali metal hydrosulfide.
    [0005]
    Method according to any one of claims 1 to 3, characterized in that the sulfide is selected from one or more in a group consisting of methyl mercaptan, ethyl thiol, methyl thioether, ethyl thioether, diphenyl thioether , dimethyl disulfide, thiofuran, hydrogen sulfide, ammonium sulfide, ammonium hydrosulfide, sodium sulfide and potassium hydrosulfide.
    [0006]
    6. Method according to claim 5, characterized by the fact that the sulfide is diphenyl thioether or dimethyl disulfide.
    [0007]
    7. Method according to claim 1, characterized by the fact that the solvent is methanol, ethanol, acetone, methyl isobutyl ketone or water.
    [0008]
    8. Method according to claim 1, characterized by the fact that the granularity of the activated carbon in the Pd / carbon catalyst is from 50 mesh to 1000 mesh; the specific surface area of the adopted activated carbon is from 600 m2 / g to 1800 m2 / g; and the amount of Pd charge is from 0.5% to 10% by weight.
    [0009]
    9. Method for preparing a p-phenylenediamine (PPD) antioxidant using 4-aminodiphenylamine (4-ADPA) and an aliphatic ketone as raw materials to prepare the PPD antioxidant characterized by the fact that the sulfur-containing Pd / carbon catalyst prepared by the method as defined in any one of claims 1 to 8 is added to the reaction system as a catalyst.
    [0010]
    10. Method according to claim 9, characterized in that the catalyst is added to the reaction system in an amount such that the weight ratio of Pd loaded in the sulfur-containing Pd / carbon catalyst to 4-ADPA is 0, 01 to 1% by weight.
    [0011]
    11. Method according to claim 9, characterized by comprising the following steps: using 4-ADPA and aliphatic ketone as raw materials, adding the sulfur-containing Pd / carbon catalyst directly to the reaction system under stirring, introducing hydrogen and synthesize the PPD antioxidant through liquid phase hydrogenation.
    [0012]
    12. Method, according to claim 9, characterized by comprising the following steps: using 4-ADPA and the aliphatic ketone as raw materials and a protonic acid or activated carbon as a catalyst, performing condensation by dehydration of 120 ° C at 150 ° C with stirring to synthesize an intermediate product; add the Pd / carbon catalyst in a reaction system formed by the intermediate product and a solvent, introduce hydrogen and synthesize the PPD antioxidant through liquid phase hydrogenation.
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    同族专利:
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    US9248443B2|2016-02-02|
    EA201400359A1|2014-09-30|
    KR102026825B1|2019-09-30|
    EP2759341A4|2015-05-06|
    CA2849561A1|2013-03-28|
    EP2759341A1|2014-07-30|
    MX2014003475A|2014-09-12|
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    ES2780388T3|2020-08-25|
    JP2014531310A|2014-11-27|
    MY165568A|2018-04-05|
    EA022735B1|2016-02-29|
    CN103008008B|2015-12-09|
    PL2759341T3|2020-07-13|
    PT2759341T|2020-04-08|
    BR112014006933A2|2017-04-04|
    CA2849561C|2019-06-11|
    CN103008008A|2013-04-03|
    EP2759341B1|2020-03-11|
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    法律状态:
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-06-11| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-11-12| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-04-07| B09A| Decision: intention to grant|
    2020-11-17| B09W| Decision of grant: rectification|Free format text: RETIFIQUE-SE, POR INCORRECOES NO QUADRO 1. |
    2021-03-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201110284001.X|2011-09-22|
    CN201110284001.XA|CN103008008B|2011-09-22|2011-09-22|The preparation method of sulfur-bearing Pd/carbon catalyst, its preparation method and p phenylenediamine type antioxidant|
    PCT/CN2012/081859|WO2013041061A1|2011-09-22|2012-09-24|Sulfur-containing palladium/carbon catalyst, preparation method therefor, and method for preparing p-phenylenediamine antioxidant|
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