CN115920926A - Preparation method and application method of ruthenium hydrogenation catalyst - Google Patents
Preparation method and application method of ruthenium hydrogenation catalyst Download PDFInfo
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Abstract
The invention relates to the field of catalyst hydrogenation, in particular to a preparation method and an application method of a ruthenium hydrogenation catalyst. The technique thereofThe key points are as follows: using Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 )H 2 W 12 O 40 ·xH 2 Precipitation deposition of O on Al 2 O 3 Modifying the carrier and then roasting to obtain a metal modified carrier; loading ruthenium by using a metal modified carrier through an impregnation method, roasting, and reducing by using hydrogen to obtain the hydrogenation catalyst; wherein, the mass fraction of ruthenium is 0.5 percent, the mass fraction of Ni is 0.5 to 2.5 percent, the mass fraction of W is 0.5 to 2.5 percent, and the rest components are alumina carriers. The invention adopts ruthenium and alumina, and auxiliary agents of nickel and tungsten respectively on the selection of active components and carriers, and the synergistic effect among several metal elements improves the dispersion degree of the active components.
Description
Technical Field
The invention relates to the field of catalyst hydrogenation, in particular to a preparation method and an application method of a ruthenium hydrogenation catalyst.
Background
Ruthenium catalysts are widely applied in the field of benzene ring hydrogenation, and compared with hydrogenation catalysts such as iron, cobalt, nickel and the like, the ruthenium catalysts have the characteristics of mild reaction conditions in hydrogenation, can generate a synergistic effect of promoting the catalytic efficiency by combining with an auxiliary agent, and are often applied in the fields of petrochemical industry, pharmaceutical synthesis and the like. With the development of new materials becoming vigorous, the requirements for the catalytic process are gradually increased, and the requirements for the performance of the catalyst are continuously improved.
In the prior art, the selected catalysts in the hydrogenation process of the benzene ring are ruthenium-carbon, ruthenium and other noble metal composite catalysts. Wherein, the total yield of the ruthenium-carbon catalyst is low and is only 63 percent; the total yield of the ruthenium and other noble metal composite catalysts can exceed 70%, but the use amount of noble metals is large, the cost of the catalysts is high, the reaction temperature is high, ester groups are easy to break, and the product purity is influenced.
In view of the defects of the prior benzene ring hydrogenation catalytic reaction, the inventor develops a preparation method and an application method of a ruthenium hydrogenation catalyst based on years of rich experience and professional knowledge of the materials and by matching theoretical analysis and research innovation.
Disclosure of Invention
The invention aims to provide a preparation method and an application method of a ruthenium hydrogenation catalyst, which respectively adopt ruthenium and alumina, and auxiliary agents of nickel and tungsten, and the synergistic action of several metal elements improves the dispersion degree of active components.
Based on the reaction kinetics principle of catalyst hydrogenation on benzene ring, hydrogen overflow occurs on the surface of catalyst in the process, that is, hydrogen is activated on the metal surface and migrates outwards from the metal surface with the aid of aromatic hydrocarbon molecules, and the overflowed hydrogen reacts with the aromatic hydrocarbon molecules at the acid position, because WOx has stronger acidity and WO x Has strong affinity to pi bond in benzene ring, and can raise the catalytic activity of the catalyst. Thus comparing with Ru/Al 2 O 3 And Ru-Ni/Al 2 O 3 More acid sites can be provided to facilitate the reaction. The addition of nickel can generate metal synergistic effect with ruthenium, the reduction temperature of NiOx is reduced, and the nickel-based auxiliary agent can promote the further complete hydrogenation of the intermediate cyclohexene substances of which the benzene rings are not completely hydrogenated, so that the hydrogenation selectivity is improved. Free RuO 2 The combination with the auxiliary oxide weakens the RuO 2 With carrier Al 2 O 3 The interaction force between the metal and the metal can be reduced, and the dispersion degree of the metal can be improved.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a ruthenium series double-promoter hydrogenation catalyst, which adopts Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 )H 2 W 12 O 40 ·xH 2 Precipitation deposition of O on Al 2 O 3 Modifying the carrier and then roasting to obtain a metal modified carrier; loading ruthenium by using a metal modified carrier through an impregnation method, roasting, and reducing by using hydrogen to obtain the hydrogenation catalyst;
wherein, the mass fraction of ruthenium is 0.5 percent, the mass fraction of Ni is 0.5 to 2.5 percent, the mass fraction of W is 0.5 to 2.5 percent, and the rest components are alumina carriers.
The catalyst obtained by one-time loading roasting is adopted to load twice, and the auxiliary agent is loaded before the active component, so that the auxiliary agent and the active component are added simultaneously, the auxiliary agent occupies active sites or covers the active component to a certain extent, the activity of the catalyst is influenced, the occurrence of the situation can be effectively avoided by two-time loading and roasting, and the catalyst can have proper texture property and mechanical strength by controlling the temperature in two-time roasting.
In the catalyst provided by the invention, the addition of the auxiliary agent improves the whole acidity of the catalyst, increases the activity of the catalyst on the reaction, makes the reaction temperature condition milder, and avoids the phenomenon of byproduct increase caused by ester bond fracture in the hydrogenation process due to temperature factors. In the same case as compared with Ru/Al 2 O 3 ，Ru-Ni/Al 2 O 3 And Ru-W/Al 2 O 3 For the catalyst, the catalytic effect of the double-auxiliary agent is better, and the sectional roasting effect of the auxiliary agent and the active component is better than the effect of one-time loading.
Further, the specific operation of the precipitation deposition method is as follows: mixing Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 )H 2 W 12 O 40 ·xH 2 Dissolving O in water to obtain mixed solution, and dissolving Al in the mixed solution 2 O 3 The carrier is added into the mixed solution for heating crystallization, and eutectic crystals can be generated at the moment, so that a synergistic effect is generated among the metal units, and the catalytic efficiency is further improved. In the invention, the ammonium metatungstate can load the auxiliary agent and can also act with the carrier, thereby further improving the pore structure of the carrier.
Further, the impregnation method comprises the following specific operations: adding RuCl 3 ·xH 2 Dissolving O in water, adding the metal modified carrier, heating and stirring to make the load of ruthenium uniform.
Further, al 2 O 3 The carrier is prepared by mixing and modifying pseudo-boehmite, citric acid, sesbania powder, methyl cellulose and water.
Further, al 2 O 3 BET specific surface area of 228.29m 2 G, pore volume of 0.61mL/g, pore diameter of 8.27nm.
Further, ruCl 3 ·xH 2 The content of Ru in O was 37.0%.
Further, (NH) 4 )H 2 W 12 O 40 ·xH 2 The W content in O was 74.6%.
Furthermore, the BET specific surface area after the hydrogenation catalyst is roasted is 190-210 m 2 G, the pore volume is 0.5-0.6 mL/g, and the pore diameter is 7.5-8.5 nm.
Further, the catalyst of the present invention is prepared according to the following steps:
s1, weighing a certain amount of Al, drying, and sieving with a 40-mesh sieve 2 O 3 The carrier is reserved, and then Ni (NO) with different qualities is weighed according to different preparation ratios 3 ) 2 .6H 2 O (Ni content 20.2%) and (NH) 4 )H 2 W 12 O 40 .xH 2 O (W content 74.6 percent) is put into a beaker, a proper amount of deionized water is added, the mixture is stirred and dissolved, and then the dried Al is slowly added into the beaker in one step 2 O 3 The carrier is stirred evenly and NH is used 4 HCO 3 Adjusting the pH value of the aqueous solution to 7-8;
s2, placing the suspension obtained in the step S1 in a water bath kettle, heating at 60-80 ℃, stirring, and crystallizing for 1-2 hours;
s3, filtering, washing and drying the solid powder obtained in the step S2, and roasting for 2-4 hours at 400-600 ℃;
s4, weighing a certain amount of RuCl in proportion 3 .xH 2 Adding a proper amount of deionized water into a beaker to dissolve O (the content of Ru is 37.0%) completely, adding the product obtained by roasting in the step S3 into the beaker to be fully stirred, placing the mixture into a water bath to be stirred so as to enable the active component to be uniformly loaded, and placing the mixture into an oven to be dried after the surface moisture is completely evaporated;
s5, roasting the solid powder obtained in the step S4 for 2-4 h at 200-400 ℃, and reducing the solid powder for 2-3 h at 200-300 ℃ in a hydrogen atmosphere after tabletting and forming to obtain the catalyst to be prepared.
The second purpose of the invention is to provide an application method of a hydrogenation catalyst, which has the same technical effect, reduces the economic requirement and is beneficial to industrialization.
The technical purpose of the invention is realized by the following technical scheme:
the application method of the hydrogenation catalyst provided by the invention uses the hydrogenation catalyst in the hydrogenation process of tetramethyl pyromellitate.
Further, the hydrogenation process of benzene ring of tetramethyl pyromellitate is carried out in a fixed bed reactor, and the process conditions are as follows: the temperature is 150-180 ℃, the pressure is 3.5-5.5 MPa, and the liquid air speed is 0.18-0.28 h -1 。
In conclusion, the invention has the following beneficial effects:
the invention adopts ruthenium and alumina, and auxiliary agents of nickel and tungsten respectively on the selection of active ingredients and a carrier, the synergistic effect among several metal elements improves the dispersion degree of the active ingredients, the addition of nickel increases the selectivity of the hydrogenation process of benzene ring, and WO x Has stronger acidity compared with Ru/Al 2 O 3 ，Ru-Ni/Al 2 O 3 Can provide more acidic sites and WO x Has strong affinity to the pi bond in benzene ring, thus being beneficial to the hydrogenation of benzene ring and improving the yield and conversion rate. And ruthenium is selected from the active component, so that the requirement on economy is reduced compared with multi-component noble metal catalysts such as ruthenium, rhodium, palladium and the like, and the method is favorable for industrialization.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the detailed description of the preparation method and the application method of the ruthenium-based hydrogenation catalyst according to the present invention is provided below.
Example 1
Preparation of hydrogenation catalyst:
s1, weighing 19.7g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O0.50 g and (NH) 4 )H 2 W 12 O 40 .xH 2 O0.13 g in a 150mL beaker and 50mL deionized water was added and stirredDissolving;
s2, slowly adding dried Al in one step 2 O 3 The carrier is stirred uniformly and then is treated with 10% NH 4 HCO 3 Adjusting the pH value of the suspension to 7-8 by using the aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder at 400 ℃ for 4 hours, and then weighing RuCl 3 ·xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then the product obtained by roasting is added into the beaker to be fully stirred and dipped;
s4, placing the mixture in a 70 ℃ water bath kettle, heating and stirring to enable the active component to be loaded more uniformly, and after the surface moisture is completely evaporated, placing the mixture in a 75 ℃ drying oven to dry for 6 hours;
s5, roasting the obtained solid powder at 200 ℃ for 3h, and reducing the solid powder at 200 ℃ for 3h in a hydrogen atmosphere after tabletting and forming to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 0.5 mass percent of nickel, 0.5 mass percent of tungsten and the balance of carrier alumina.
Example 2
Preparation of hydrogenation catalyst:
s1, weighing 19.7g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O0.50 g and (NH) 4 )H 2 W 12 O 40 .xH 2 0.13g of O is put into a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding dried Al in one step 2 O 3 The carrier is stirred uniformly and then is treated with 10% NH 4 HCO 3 Adjusting the pH value of the suspension to 7-8 by using the aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is used for overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder for 3 hours at 500 ℃, and weighing RuCl 3 ·xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then a product obtained by roasting is added into the beaker to be fully stirred and dipped;
s4, placing the mixture in a 70 ℃ water bath kettle, heating and stirring the mixture to enable the active component to be loaded more uniformly, and after the surface moisture is completely evaporated, placing the mixture in a 75 ℃ drying oven to dry the mixture for 6 hours;
s5, roasting the obtained solid powder at 300 ℃ for 3h, and reducing the solid powder for 3h at 250 ℃ in a hydrogen atmosphere after tabletting and forming to obtain a catalyst;
the active components of the catalyst comprise 0.5 percent of ruthenium, 0.5 percent of nickel, 0.5 percent of tungsten and the balance of carrier alumina.
Example 3
Preparation of hydrogenation catalyst:
s1, weighing 19.7g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O0.50 g and (NH) 4 )H 2 W 12 O 40 ·xH 2 0.13g of O is put in a 150mL beaker, and 50mL of deionized water is added for stirring and dissolving;
s2, slowly adding the dried Al in one step 2 O 3 Stirring the carrier uniformly, then adding 10% of NH 4 HCO 3 Adjusting the pH value of the suspension to 7-8 with an aqueous solution, placing the suspension in a 70 ℃ water bath kettle, stirring, heating and crystallizing for 1h, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6h, and roasting the solid powder at 600 ℃ for 2h;
s3, then weighing RuCl 3 ·xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then a product obtained by roasting is added into the beaker to be fully stirred and dipped;
s4, placing the mixture in a 70 ℃ water bath kettle, heating and stirring to enable the active component to be loaded more uniformly, and after the surface moisture is completely evaporated, placing the mixture in a 75 ℃ drying oven to dry for 6 hours;
s5, roasting the obtained solid powder at 400 ℃ for 2h, tabletting and reducing the solid powder at 300 ℃ for 2h in a hydrogen atmosphere to obtain the catalyst.
The active components of the catalyst comprise 0.5 percent of ruthenium, 0.5 percent of nickel, 0.5 percent of tungsten and the balance of carrier alumina.
Example 4
Preparation of hydrogenation catalyst:
s1, weighing 19.3g of alumina carrierWeighing Ni (NO) for use 3 ) 2 ·6H 2 O1.49 g and (NH) 4 )H 2 W 12 O 40 ·xH 2 0.40g of O is put in a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding the dried Al in one step 2 O 3 Stirring the carrier uniformly, then adding 10% of NH 4 HCO 3 Adjusting the pH of the suspension to 7-8 by using an aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder at 400 ℃ for 4 hours, and then weighing RuCl 3 ·xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then a product obtained by roasting is added into the beaker to be fully stirred and dipped;
s4, placing the mixture in a 70 ℃ water bath kettle, heating and stirring to enable the active component to be loaded more uniformly, and after the surface moisture is completely evaporated, placing the mixture in a 75 ℃ drying oven to dry for 6 hours;
s5, roasting the obtained solid powder at 200 ℃ for 3h, and reducing the solid powder at 200 ℃ for 3h in a hydrogen atmosphere after tabletting and forming to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 1.5 mass percent of nickel, 1.5 mass percent of tungsten and the balance of carrier alumina.
Example 5
Preparation of hydrogenation catalyst:
s1, weighing 19.3g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O1.49 g and (NH) 4 )H 2 W 12 O 40 ·xH 2 0.40g of O is put in a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding the dried Al in one step 2 O 3 Stirring the carrier uniformly, then adding 10% of NH 4 HCO 3 Adjusting the pH of the suspension to 7-8 by using an aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder for 3 hours at 500 ℃, and thenWeighing RuCl 3 ·xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then the product obtained by roasting is added into the beaker to be fully stirred and dipped;
s4, placing the mixture in a 70 ℃ water bath kettle, heating and stirring to enable the active component to be loaded more uniformly, and after the surface moisture is completely evaporated, placing the mixture in a 75 ℃ drying oven to dry for 6 hours;
s5, roasting the obtained solid powder at 300 ℃ for 3h, and reducing the solid powder at 250 ℃ for 3h in a hydrogen atmosphere after tabletting and forming to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 1.5 mass percent of nickel, 1.5 mass percent of tungsten and the balance of carrier alumina.
Example 6
Preparation of hydrogenation catalyst:
s1, weighing 19.3g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O1.49 g and (NH) 4 )H 2 W 12 O 40 ·xH 2 0.40g of O is put in a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding dried Al in one step 2 O 3 Stirring the carrier uniformly, then adding 10% of NH 4 HCO 3 Adjusting the pH value of the suspension to 7-8 by using the aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder at 600 ℃ for 2 hours, and then weighing RuCl 3 ·xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then a product obtained by roasting is added into the beaker to be fully stirred and dipped;
s4, placing the mixture in a 70 ℃ water bath kettle, heating and stirring to enable the active component to be loaded more uniformly, and after the surface moisture is completely evaporated, placing the mixture in a 75 ℃ drying oven to dry for 6 hours;
s5, roasting the obtained solid powder at 400 ℃ for 2h, tabletting and reducing the solid powder at 300 ℃ for 2h in a hydrogen atmosphere to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 1.5 mass percent of nickel, 1.5 mass percent of tungsten and the balance of carrier alumina.
Example 7
Preparation of hydrogenation catalyst:
s1, weighing 18.9g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O2.48 g and (NH) 4 )H 2 W 12 O 40 ·xH 2 0.67g of O is put into a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding the dried Al in one step 2 O 3 Stirring the carrier uniformly, then adding 10% of NH 4 HCO 3 Adjusting the pH value of the suspension to 7-8 by using the aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder at 400 ℃ for 4 hours, and then weighing RuCl 3 .xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then the product obtained by roasting is added into the beaker to be fully stirred and dipped;
s4, placing the mixture in a 70 ℃ water bath kettle, heating and stirring to enable the active component to be loaded more uniformly, and after the surface moisture is completely evaporated, placing the mixture in a 75 ℃ drying oven to dry for 6 hours;
s5, roasting the obtained solid powder at 200 ℃ for 3h, and reducing the solid powder at 200 ℃ for 3h in a hydrogen atmosphere after tabletting and forming to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 2.5 mass percent of nickel, 2.5 mass percent of tungsten and the balance of carrier alumina.
Example 8
Preparation of hydrogenation catalyst:
s1, weighing 18.9g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O2.48 g and (NH) 4 )H 2 W 12 O 40 ·xH 2 0.67g of O is put into a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding the dried Al in one step 2 O 3 The carrier is stirred uniformly and then is treated with 10% NH 4 HCO 3 Aqueous solution conditioning suspensionPh is 7-8, and the suspension is placed in a water bath kettle at 70 ℃ to be stirred, heated and crystallized for 1 hour;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder at 500 ℃ for 3 hours, and then weighing RuCl 3 ·xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then the product obtained by roasting is added into the beaker to be fully stirred and dipped;
s4, placing the mixture in a 70 ℃ water bath kettle, heating and stirring to enable the active component to be loaded more uniformly, and after the surface moisture is completely evaporated, placing the mixture in a 75 ℃ drying oven to dry for 6 hours;
s5, roasting the obtained solid powder at 300 ℃ for 3h, and reducing the solid powder at 250 ℃ for 3h in a hydrogen atmosphere after tabletting and forming to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 2.5 mass percent of nickel, 2.5 mass percent of tungsten and the balance of carrier alumina.
Example 9
Preparation of hydrogenation catalyst:
s1, weighing 18.9g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O2.48 g and (NH) 4 )H 2 W 12 O 40 ·xH 2 0.67g of O is put into a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding the dried Al in one step 2 O 3 The carrier is stirred uniformly and then is treated with 10% NH 4 HCO 3 Adjusting the pH value of the suspension to 7-8 by using the aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder at 600 ℃ for 2 hours, and weighing RuCl 3 ·xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then the product obtained by roasting is added into the beaker to be fully stirred and dipped;
s4, placing the mixture in a 70 ℃ water bath kettle, heating and stirring the mixture to enable the active component to be loaded more uniformly, and after the surface moisture is completely evaporated, placing the mixture in a 75 ℃ drying oven to dry the mixture for 6 hours;
s5, roasting the obtained solid powder at 400 ℃ for 2h, tabletting and reducing the solid powder at 300 ℃ for 2h in a hydrogen atmosphere to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 2.5 mass percent of nickel, 2.5 mass percent of tungsten and the balance of carrier alumina.
Performance analysis
The characterization and analysis of the hydrogenation catalysts of examples 1 to 9 are shown in tables 1 to 3.
TABLE 1 pore Structure of hydrogenation catalysts of examples 1-9
| Examples | Specific surface area m 2 /g | Pore volume cm 3 /g | Pore size nm |
| 1 | 199.77 | 0.58 | 8.44 |
| 2 | 201.34 | 0.59 | 8.44 |
| 3 | 203.04 | 0.59 | 8.34 |
| 4 | 194.62 | 0.59 | 8.37 |
| 5 | 196.43 | 0.59 | 8.39 |
| 6 | 203.67 | 0.59 | 8.33 |
| 7 | 193.41 | 0.57 | 8.30 |
| 8 | 194.85 | 0.57 | 8.28 |
| 9 | 196.25 | 0.58 | 8.28 |
| Carrier Al 2 O 3 | 228.29 | 0.61 | 8.27 |
TABLE 2 examples 1-9 catalyst compositions and preparation
| Examples | Composition (except carrier) | First stage roasting | Two stage roasting | Reduction of |
| 1 | 0.5Ru％，0.5Ni％，0.5％W | 400℃，4h | 200℃，3h | 200℃，3h |
| 2 | 0.5Ru％，0.5Ni％，0.5％W | 500℃，3h | 300℃，3h | 250℃，3h |
| 3 | 0.5Ru％，0.5Ni％，0.5％W | 600℃，2h | 400℃，2h | 300℃，2h |
| 4 | 0.5Ru％，1.5Ni％，1.5％W | 400℃，4h | 200℃，3h | 200℃，3h |
| 5 | 0.5Ru％，1.5Ni％，1.5％W | 500℃，3h | 300℃，3h | 250℃，3h |
| 6 | 0.5Ru％，1.5Ni％，1.5％W | 600℃，2h | 400℃，2h | 300℃，2h |
| 7 | 0.5Ru％，2.5Ni％，2.5％W | 400℃，4h | 200℃，3h | 200℃，3h |
| 8 | 0.5Ru％，2.5Ni％，2.5％W | 500℃，3h | 300℃，3h | 250℃，3h |
| 9 | 0.5Ru％，2.5Ni％，2.5％W | 600℃，2h | 400℃，2h | 300℃，2h |
44.8g of pyromellitic acid tetramethyl ester is dissolved in 500mL of 1, 4-dioxane to prepare a solution with the mass fraction of 8 percent as the raw material of the hydrogenation reaction. And then, filling a catalyst into the single-tube fixed bed reactor, setting a program for heating and reducing in a hydrogen atmosphere, and conveying the raw materials into the reactor through a metering pump after the reduction is finished. Reaction conditions are as follows: the temperature is 160 ℃, the pressure is 4.5MPa, and the liquid air speed is 0.28h -1 Hydrogen to oil volume ratio of 696, and after the reaction stabilized, a sample was taken for chromatographic analysis. The catalysts of examples 1 to 9 were evaluated for hydrogenation performance as shown in Table 3 below.
TABLE 3 evaluation of hydrogenation Activity of catalyst
| Examples | Conversion rate/% | Selectivity/%) |
| 1 | 99.1 | 97.2 |
| 2 | 99.6 | 98.8 |
| 3 | 99.3 | 98.8 |
| 4 | 99.9 | 99.1 |
| 5 | 99.9 | 99.1 |
| 6 | 99.9 | 99.4 |
| 7 | 99.1 | 98.1 |
| 8 | 99.2 | 98.3 |
| 9 | 99.2 | 98.4 |
Comparative example 1
S1, weighing 19.3g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O1.49 g and (NH) 4 )H 2 W 12 O 40 ·xH 2 0.40g of O is put in a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding the dried Al in one step 2 O 3 The carrier is stirred uniformly and then is treated with 10% NH 4 HCO 3 Adjusting the pH value of the suspension to 7-8 by using the aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder at 500 ℃ for 3 hours, and then weighing RuCl 3 ·xH 2 0.27g of O is put into a 100mL beaker, 15mL of deionized water is added to dissolve completely, and then the product obtained by roasting is added into the beaker to be fully stirred and dipped;
s3, heating and stirring the mixture in a 70 ℃ water bath to enable the active component to be loaded more uniformly, and drying the mixture in a 75 ℃ drying oven for 6 hours after the surface moisture is completely evaporated;
and S4, roasting the obtained solid powder at 300 ℃ for 3h, and reducing the solid powder at 250 ℃ for 3h in a hydrogen atmosphere after tabletting and forming to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 1.5 mass percent of nickel, 1.5 mass percent of tungsten and the balance of carrier alumina.
Comparative example 2
S1, weighing 19.3g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O 1.49g，(NH 4 )H 2 W 12 O 40 ·xH 2 O 0.40g，RuCl 3 .xH 2 0.27g of O is put in a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding dried Al in one step 2 O 3 The carrier is stirred uniformly and then is treated with 10% NH 4 HCO 3 Adjusting the pH value of the suspension to 7-8 by using the aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder for 3 hours at 300 ℃, tabletting the roasted solid powder, and reducing the pressed solid powder for 3 hours at 250 ℃ in a hydrogen atmosphere to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 1.5 mass percent of nickel, 1.5 mass percent of tungsten and the balance of carrier alumina.
Comparative example 3
19.6g of alumina carrier are first weighed out for further use, and then Ni (NO) is weighed out 3 ) 2 .6H 2 O1.49 g is put into a 150mL beaker, 18mL of deionized water is added, the mixture is stirred and dissolved, and then the mixture is placed into a 70 ℃ water bath kettle to which dried Al is added 2 O 3 Stirring the carrier uniformly, putting the carrier into a 75 ℃ oven for drying treatment for 6h after the surface moisture is completely evaporated, roasting the obtained solid powder for 3h at 500 ℃, and then weighing RuCl 3 .xH 2 O0.27g is put into a 150mL beaker, 18mL deionized water is added to dissolve the mixture completely, the roasted solid powder is added to be stirred uniformly, and then the mixture is put into a 70 ℃ water bath kettle to be heated and stirred so as to ensure the activityThe component loading is more uniform, the obtained solid powder is roasted for 3h at 300 ℃ after the surface moisture is completely evaporated and is put into a 75 ℃ oven for drying for 6h, and the obtained solid powder is reduced for 3h at 250 ℃ in a hydrogen atmosphere after the roasting is finished, so that the catalyst is obtained. The active components of the catalyst comprise 0.5 mass percent of ruthenium, 1.5 mass percent of nickel and the balance of carrier alumina.
Comparative example 3
S1, weighing 19.6g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O1.49 g is put into a 150mL beaker, 18mL of deionized water is added, and the mixture is stirred and dissolved;
s2, placing the mixture in a water bath kettle at 70 ℃, and adding dried Al 2 O 3 Uniformly stirring the carrier, and drying in a 75 ℃ drying oven for 6 hours after the surface moisture is completely evaporated;
s3, roasting the obtained solid powder at 500 ℃ for 3h, and then weighing RuCl 3 ·xH 2 Adding 0.27g of O into a 150mL beaker, adding 18mL of deionized water, completely dissolving, adding the roasted solid powder, and uniformly stirring;
s4, heating and stirring the mixture in a 70 ℃ water bath to enable the active component to be loaded more uniformly, and drying the mixture in a 75 ℃ drying oven for 6 hours after the surface moisture is completely evaporated;
s5, roasting the obtained solid powder at 300 ℃ for 3h, and reducing the solid powder at 250 ℃ for 3h in a hydrogen atmosphere after roasting to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 1.5 mass percent of nickel and the balance of carrier alumina.
Comparative example 4
S1, weighing 19.3g of alumina carrier for later use, and then weighing Ni (NO) 3 ) 2 ·6H 2 O 1.49g，RuCl 3 ·xH 2 O0.27g is put into a 150mL beaker, 18mL of deionized water is added, and the mixture is stirred and dissolved;
s2, placing the mixture in a water bath kettle at 70 ℃, and adding dried Al 2 O 3 Uniformly stirring the carrier, putting the carrier into a 75 ℃ oven for drying for 6h after the surface moisture is completely evaporated, and roasting for 3h at 300 ℃;
and S3, after roasting is finished, reducing for 3 hours at 250 ℃ in a hydrogen atmosphere to obtain the catalyst.
The active components of the catalyst comprise 0.5 mass percent of ruthenium, 1.5 mass percent of nickel and the balance of carrier alumina.
Comparative example 5
S1, weighing 19.3g of alumina carrier for later use, and then weighing (NH) 4 )H 2 W 12 O 40 .xH 2 O 0.40g，RuCl 3 ·xH 2 0.27g of O is put in a 150mL beaker, and 50mL of deionized water is added to be stirred and dissolved;
s2, slowly adding the dried Al in one step 2 O 3 The carrier is stirred uniformly and then is treated with 10% NH 4 HCO 3 Adjusting the pH value of the suspension to 7-8 by using the aqueous solution, and placing the suspension in a water bath kettle at 70 ℃ for stirring, heating and crystallizing for 1h;
s3, filtering and washing the obtained solid powder after the solid powder is kept overnight, drying the solid powder in a 75 ℃ oven for 6 hours, roasting the solid powder for 3 hours at 300 ℃, tabletting the roasted solid powder, and reducing the pressed solid powder for 3 hours at 250 ℃ in a hydrogen atmosphere to obtain the catalyst.
The active component of the catalyst comprises 0.5 mass percent of ruthenium, 1.5 mass percent of tungsten and the balance of carrier alumina.
Comparative example 6
S1, weighing 19.9g of alumina carrier for later use, and then weighing RuCl 3 ·xH 2 O0.27g in a 150mL beaker, 18mL deionized water was added to dissolve completely, and then dried Al was added 2 O 3 Stirring the carrier;
s2, heating and stirring the mixture in a 70 ℃ water bath to enable the active component to be loaded more uniformly, and drying the mixture in a 75 ℃ drying oven for 6 hours after the surface moisture is completely evaporated;
s3, roasting the obtained solid powder at 300 ℃ for 3h, and reducing the solid powder at 250 ℃ for 3h in a hydrogen atmosphere after roasting to obtain the catalyst.
The active component ruthenium content is 0.5 percent, and the rest is carrier alumina.
Comparative test of hydrogenation Activity
44.8g of tetramethylpyromellitate are dissolved in 500mL of 1, 4-dioxane to prepare a solution with the mass fraction of 8 percentRaw material for hydrogenation reaction. And then, filling a catalyst into the single-tube fixed bed reactor, setting a program for heating and reducing in a hydrogen atmosphere, and conveying the raw materials into the reactor through a metering pump after the reduction is finished. Reaction conditions are as follows: the temperature is 160 ℃, the pressure is 4.5MPa, and the liquid air speed is 0.28h -1 Hydrogen to oil volume ratio of 696, and after the reaction stabilized, a sample was taken for chromatographic analysis. The pore structure analysis and the catalyst hydrogenation performance evaluation of the catalysts under different loading, roasting conditions and preparation modes are compared as follows.
TABLE 4 analysis of pore structures of catalysts of comparative examples 1 to 6
| Catalyst and process for producing the same | Specific surface area m 2 /g | Pore volume cm 3 /g | Pore size nm |
| C1 | 194.62 | 0.59 | 8.39 |
| C2 | 179.25 | 0.56 | 8.11 |
| C3 | 203.67 | 0.60 | 8.33 |
| C4 | 199.62 | 0.59 | 8.21 |
| C5 | 201.43 | 0.59 | 8.25 |
| C6 | 211.41 | 0.60 | 8.30 |
| Carrier Al 2 O 3 | 228.29 | 0.61 | 8.27 |
TABLE 5 comparative examples 1-6 catalyst compositions and preparation
TABLE 6 evaluation of hydrogenation activity of catalysts of comparative examples 1 to 6
| Catalyst and process for preparing same | Conversion rate/% | Selectivity/%) |
| C1 | 99.9 | 99.1 |
| C2 | 88.2 | 90.2 |
| C3 | 99.7 | 96.2 |
| C4 | 89.9 | 90.9 |
| C5 | 95.4 | 90.2 |
| C6 | 99.9 | 93.7 |
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A process for preparing the dual-assistant Ru-series hydrocatalyst features use of Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 )H 2 W 12 O 40 ·xH 2 Precipitation deposition of O on Al 2 O 3 Modifying the carrier and then roasting to obtain a metal modified carrier; loading ruthenium by using a metal modified carrier through an impregnation method, roasting, and reducing by using hydrogen to obtain the hydrogenation catalyst;
wherein, the mass fraction of ruthenium is 0.45-0.55%, the mass fraction of Ni is 0.5-2.5%, the mass fraction of W is 0.5-2.5%, and the rest is alumina carrier.
2. The preparation method of the ruthenium-based double-promoter hydrogenation catalyst according to claim 1, wherein the precipitation deposition method comprises the following specific operations: mixing Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 )H 2 W 12 O 40 ·xH 2 Dissolving O in water to obtain mixed solution, and dissolving Al in the mixed solution 2 O 3 And adding the carrier into the mixed solution for heating crystallization.
3. The preparation method of ruthenium dual-promoter hydrogenation catalyst according to claim 1 or 2, wherein the impregnation method comprises the following specific operations: adding RuCl 3 ·xH 2 Dissolving O in water, adding the metal modified carrier, heating and stirring to make the load of ruthenium uniform.
4. The method for preparing the ruthenium-based double-promoter hydrogenation catalyst as claimed in claim 1, wherein the Al is 2 O 3 The carrier is prepared by mixing and modifying pseudo-boehmite, citric acid, sesbania powder, methyl cellulose and water.
5. The method of claim 1, wherein the Al is added in the hydrogenation catalyst 2 O 3 The BET specific surface area of the carrier is 220.00 to 230.00m 2 (iv)/g, pore volume 0.55 to 0.65mLg, the pore diameter is 8.1 to 8.3nm.
6. The method for preparing ruthenium dual promoter hydrogenation catalyst as claimed in claim 1, wherein the RuCl is added 3 ·xH 2 The content of Ru in O is 35.0-37.0%.
7. The method for preparing a ruthenium-based double promoter hydrogenation catalyst as claimed in claim 1, wherein the (NH) 4 )H 2 W 12 O 40 ·xH 2 The W content in O was 74.6%.
8. The preparation method of a ruthenium double-promoter hydrogenation catalyst as claimed in claim 1, wherein the BET specific surface area of the calcined hydrogenation catalyst is 190 to 210m 2 The pore volume is 0.5 to 0.6mL/g, and the pore diameter is 7.5 to 8.5nm.
9. The application method of the hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 8, wherein the hydrogenation catalyst is used in a hydrogenation process of tetramethyl pyromellitate.
10. The application method of the hydrogenation catalyst according to claim 9, wherein the process conditions of the hydrogenation process are as follows: the temperature is 150 to 180 ℃, the pressure is 3.5 to 5.5MPa, and the liquid air speed is 0.18 to 0.28h -1 。
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