CN113244918A - Ruthenium-based carrier type hydrogenation catalyst, and preparation method and application thereof - Google Patents
Ruthenium-based carrier type hydrogenation catalyst, and preparation method and application thereof Download PDFInfo
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- CN113244918A CN113244918A CN202110593672.8A CN202110593672A CN113244918A CN 113244918 A CN113244918 A CN 113244918A CN 202110593672 A CN202110593672 A CN 202110593672A CN 113244918 A CN113244918 A CN 113244918A
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a ruthenium-based carrier type hydrogenation catalyst and a preparation method and application thereof, wherein the ruthenium-based carrier type hydrogenation catalyst comprises an active component, a carrier, a first auxiliary agent and a second auxiliary agent, the active component is ruthenium salt, the carrier is zirconium oxide, the first auxiliary agent is zinc salt, the second auxiliary agent is molybdenum salt, and the first auxiliary agent accounts for 0.85-2.55% of the catalyst and the second auxiliary agent accounts for 0.017-0.085% of the catalyst in percentage by mass. The catalyst of the invention has strong capability of resisting fluctuation of process conditions, can be recovered to a normal state in a short time when the process conditions are greatly changed, and is beneficial to maintaining the stability of production. Compared with a metal catalyst, the catalyst has simple regeneration steps and is easy to realize industrialization. Solves the technical problems of low benzene conversion, poor cyclohexene selectivity and low catalytic activity of the catalyst used for preparing cyclohexene by hydrogenation of ruthenium chloride type benzene.
Description
Technical Field
The invention relates to the field of cyclohexene preparation by benzene hydrogenation, in particular to a ruthenium-based carrier type hydrogenation catalyst, and a preparation method and application thereof.
Background
Cyclohexene is an important organic intermediate, is widely used for the production of adipic acid, nylon-6, nylon-66, polyamide and other fine chemicals, and has huge industrial economic value and wide market prospect. Due to the wide use of cyclohexene as a raw material, further development of more economical and green cyclohexene production routes has been of great interest. The benzene has low price and rich source, and can be used for directly synthesizing cyclohexene. Thermodynamically, however, the free energy change for the production of cyclohexene from the hydrogenation of benzene is much smaller than the free energy change for the production of cyclohexane. Thus, in the reaction of benzene hydrogenation, the reaction equilibrium tends to produce more thermodynamically stable cyclohexane; from the view of the reactivity of the substrate, benzene is a typical aromatic ring and has higher chemical stability. Cyclohexene has a non-conjugated carbon-carbon double bond, which is much more reactive than the conjugated double bond of aromatic nature of the benzene ring. Therefore, on the catalyst, the cyclohexene has higher activity and is easier to carry out hydrogenation reaction. Even if cyclohexene is produced in the reaction, if the cyclohexene cannot be rapidly desorbed from the catalyst, the benzene hydrogenation reaction is difficult to stay in the stage of producing cyclohexene. Therefore, the development of a catalyst with high activity and high cyclohexene selectivity is a research focus.
Most of catalysts used in the prior preparation of cyclohexene by benzene hydrogenation are metal catalysts, the metal catalysts have poor stability, and in the production and use processes, active metals of the catalysts are easy to separate from auxiliary metals when meeting acid, so that the catalysts are pulverized, the reaction conversion rate and selectivity are reduced sharply, and the pulverized catalysts float and are easy to run off; secondly, in the use process of the ruthenium chloride catalyst, zirconium oxide is required to be added as a dispersing agent to prevent the catalyst from agglomerating, and the dispersing effect is difficult to control, so that the conversion rate and the selectivity of the hydrogenation reaction are influenced, and the industrial production is greatly limited.
Disclosure of Invention
The invention aims to solve the technical problems of low benzene conversion, poor cyclohexene selectivity and low catalytic activity of the existing catalyst for preparing cyclohexene by hydrogenating ruthenium chloride type benzene.
In order to solve the technical problems, the invention adopts the following technical scheme:
a ruthenium-based carrier type hydrogenation catalyst is developed and comprises an active component, a carrier, a first auxiliary agent and a second auxiliary agent, wherein the active component is ruthenium salt, the carrier is zirconium oxide, the first auxiliary agent is zinc salt, the second auxiliary agent is molybdenum salt, and the first auxiliary agent accounts for 0.85-2.55% of the catalyst and the second auxiliary agent accounts for 0.017-0.085% of the catalyst in percentage by mass.
Preferably, the ruthenium salt accounts for 14-16% of the weight of the catalyst in percentage by mass.
Preferably, the zirconia accounts for 82-85% of the weight of the catalyst in percentage by mass.
Preferably, the ruthenium salt is ruthenium chloride, the zinc salt is zinc sulfate, and the molybdenum salt is sodium molybdate.
The preparation method of the aqueous solution of the ruthenium-based carrier hydrogenation catalyst comprises the following steps:
1) adding ruthenium salt, zinc salt, molybdenum salt and a zirconia carrier into water to prepare a metal salt solution;
2) adjusting the pH of the metal salt solution by using an alkali liquor to ensure that the pH of the metal salt solution is not less than 10; stirring simultaneously to carry out precipitation reaction;
3) after the precipitation reaction is finished, the reaction solution is contacted with hydrogen to carry out reduction reaction;
4) and after the reduction reaction is finished, cooling and washing the reaction solution to obtain the ruthenium-based carrier type hydrogenation catalyst aqueous solution.
Preferably, in step 1), the ruthenium salt, the zinc salt, the molybdenum salt and the zirconia support are mixed with water in a mass ratio of 1: 6.
Preferably, in the step 2), the precipitation reaction temperature is 50-80 ℃, and the precipitation reaction time is 1-2 h; in the step 2), the mass ratio of the metal salt solution to the alkali liquor is 1: 0.6 to 1.2; the alkali liquor is a sodium hydroxide aqueous solution, and the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 10-15%.
Preferably, in the step 3), the reduction reaction temperature is 110-160 ℃, the reduction reaction time is 10-15 h, and the hydrogen pressure is 3-5 MPa.
Preferably, in step 4), the temperature of the reaction solution is reduced to not higher than 80 ℃, and the reaction solution is washed with water until the pH value is 7-8.
An application of the ruthenium-based carrier type hydrogenation catalyst in preparation of cyclohexene by partial hydrogenation of benzene.
Compared with the prior art, the invention has the beneficial technical effects that:
1. in the process of preparing cyclohexene by hydrogenating benzene, the ruthenium-based carrier type hydrogenation catalyst is prepared by mutually matching ruthenium chloride serving as an active component, zinc sulfate serving as a first auxiliary agent, sodium molybdate serving as a second auxiliary agent and zirconium oxide serving as a carrier, so that the catalytic activity of the catalyst can be effectively improved, and each gram of the catalyst can convert up to 200 grams of benzene within 1 hour, which is far higher than the average level of 100 grams of benzene at present in China. The carrier zirconia is added in the invention, so that the agglomeration of the catalyst can be prevented, and a higher effective reaction area is kept; under the condition of keeping the cyclohexene selectivity not lower than 80%, the benzene conversion rate can reach 70%;
in addition, the ruthenium-based carrier type hydrogenation catalyst has long service life, and because the carrier zirconia is added in the catalyst manufacturing process, the catalyst agglomeration is prevented, and the effective reaction time of the catalyst is prolonged; the service life of the catalyst is measured by the consumption of the catalyst per ton of product, and 2.9 g of catalyst per ton of product is originally designed, so that the product can greatly increase 2.0 g of catalyst per ton of product; the catalyst has strong anti-poisoning capacity, and compared with a ruthenium chloride catalyst, the catalyst has good settling property, is simple to wash and small in corrosion to equipment, and avoids excessive loss of the catalyst. Meanwhile, the catalyst has strong anti-fluctuation capability of process conditions, can be recovered to a normal state in a short time when the process conditions are greatly changed, and is favorable for maintaining the stability of production. Compared with a metal catalyst, the catalyst has simple regeneration steps and is easy to realize industrialization.
2. According to the invention, molybdenum with a specific ratio is used as a second auxiliary agent, and a specific active component and a first auxiliary agent are matched, so that the catalytic activity of the catalyst can be further improved, and higher benzene conversion rate and cyclohexene selectivity are maintained.
3. Compared with a metal catalyst, the carrier type catalyst provided by the invention does not need to be added with dispersant zirconium oxide in the production and use processes, so that the reaction effect is more stable and the loss is not easy to occur.
4. The preparation method of the ruthenium-based carrier type hydrogenation catalyst provided by the invention has the advantages that the prepared multi-element ruthenium-based catalyst has uniform particle size distribution, long service life and strong poisoning resistance, can still maintain the normal operation of production under the condition of short-term inactivation of the desulfurization catalyst, has good settling property, simple washing and small corrosion to equipment compared with a metal type catalyst, avoids excessive loss of the catalyst, has strong fluctuation resistance of process conditions, can recover to a normal state in a short time when the process conditions are greatly changed, is favorable for maintaining the stability of production, has simple regeneration steps compared with a carrier type catalyst, and is easy to realize industrialization.
Drawings
FIG. 1 is a graph of benzene conversion over time using a comparative catalyst;
FIG. 2 is a graph of cyclohexene selectivity of benzene as a function of benzene conversion using a comparative catalyst;
FIG. 3 is a graph of benzene conversion over time using the catalyst of the present invention;
FIG. 4 is a graph of cyclohexene selectivity as a function of benzene conversion using the inventive catalyst.
Detailed Description
The following examples are intended to illustrate the present invention in detail and should not be construed as limiting the scope of the present invention in any way. The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the industrial raw materials (reagents and raw materials are selected according to the situation) are all conventional industrial raw materials which are sold in the market if not specified; the processing and manufacturing methods (detection, test, preparation method and the like are selected according to the situation) are conventional methods unless otherwise specified.
Example 1: a ruthenium-based carrier type hydrogenation catalyst comprises the following raw materials in percentage by mass: comprises 15 percent of ruthenium chloride, 83.5 percent of zirconium oxide, 1.4 percent of zinc sulfate and 0.085 percent of sodium molybdate.
The preparation method of the aqueous solution of the ruthenium-based carrier hydrogenation catalyst comprises the following steps:
1) mixing ruthenium salt, zinc salt, molybdenum salt, zirconia carrier and water in a mass ratio of 1:6 to prepare a metal salt solution;
2) adjusting the pH of the metal salt solution by using an alkali liquor to ensure that the pH of the metal salt solution is not less than 10; stirring simultaneously to carry out precipitation reaction; the precipitation reaction temperature is 60 ℃, and the precipitation reaction time is 1.5 h; the mass ratio of the metal salt solution to the alkali liquor is 1: 1; the alkali liquor is a sodium hydroxide aqueous solution, and the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 12%;
3) after the precipitation reaction is finished, the reaction solution is contacted with hydrogen to carry out reduction reaction; the reduction reaction temperature is 120 ℃, the reduction reaction time is 12h, and the hydrogen pressure is 5 MPa;
4) after the reduction reaction is finished, cooling and washing the reaction solution to obtain a ruthenium-based carrier type hydrogenation catalyst aqueous solution; and cooling the reaction liquid to 40 ℃, and washing the reaction liquid with water until the pH value is 7-8.
Example 2: the difference from example 1 is that:
a ruthenium-based carrier type hydrogenation catalyst comprises the following raw materials in percentage by mass: comprises 16 percent of ruthenium chloride, 83 percent of zirconium oxide, 0.99 percent of zinc sulfate and 0.075 percent of sodium molybdate.
Example 3: the difference from example 1 is that:
a ruthenium-based carrier type hydrogenation catalyst comprises the following raw materials in percentage by mass: comprises 14 percent of ruthenium chloride, 84 percent of zirconium oxide, 1.9 percent of zinc sulfate and 0.075 percent of sodium molybdate.
Example 4: the difference from example 1 is that:
a preparation method of an aqueous solution of a ruthenium-based carrier hydrogenation catalyst comprises the following steps:
1) mixing ruthenium salt, zinc salt, molybdenum salt, zirconia carrier and water in a mass ratio of 1:6 to prepare a metal salt solution;
2) adjusting the pH of the metal salt solution by using an alkali liquor to ensure that the pH of the metal salt solution is not less than 10; stirring simultaneously to carry out precipitation reaction; the precipitation reaction temperature is 70 ℃, and the precipitation reaction time is 1 h; the mass ratio of the metal salt solution to the alkali liquor is 1: 0.8; the alkali liquor is a sodium hydroxide aqueous solution, and the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 15%;
3) after the precipitation reaction is finished, the reaction solution is contacted with hydrogen to carry out reduction reaction; the reduction reaction temperature is 150 ℃, the reduction reaction time is 14h, and the hydrogen pressure is 4 MPa;
4) after the reduction reaction is finished, cooling and washing the reaction solution to obtain a ruthenium-based carrier type hydrogenation catalyst aqueous solution; and cooling the reaction liquid to 40 ℃, and washing the reaction liquid with water until the pH value is 7-8.
Example 5: the difference from example 1 is that:
an application of the ruthenium-based carrier type hydrogenation catalyst in preparation of cyclohexene by partial hydrogenation of benzene.
Example of effects: 1. while the operation described in example 1 was being performed, control 1 was set up, the conditions of control 1 were kept consistent except for the inconsistency of the components, and the partial hydrogenation of liquid-phase benzene as component of control 1 was carried out in a limbo mini autoclave reactor of Buchiglaster corporation, 1.000 gRu-based catalyst (containing about Ru0.048 g), 58 mLH2O，8.786g ZnSO4·7H2O; pre-reducing at 140 ℃ under the conditions of stirring speed of 900r ∙ min < -1 > and hydrogen pressure of 5 MPa; adding 29mL of benzene which is heated to 140 ℃, adjusting the rotation speed to 1200r ∙ min < -1 > and starting the reaction timing. The product composition, benzene conversion and cyclohexene selectivity were analyzed using a gas chromatograph FID detector with reference to fig. 1 to 4.
TABLE 1 Effect of comparative catalysts on partial hydrogenation of benzene to cyclohexene
TABLE 2 influence of comparative catalysts on the partial hydrogenation of benzene to cyclohexene
Gamma value: at a certain conversion of benzene, one gram of catalyst can convert several grams of benzene per hour, representing the catalyst activity, the greater this value, the higher the catalyst activity.
From tables 1-2 and FIGS. 1-4, it can be seen that the hydrogenation catalyst produced by the Tuo blue technology, regardless of the reactivity or selectivity, is significantly improved compared with other similar hydrogenation catalysts.
While the present invention has been described in detail with reference to the drawings and the embodiments, those skilled in the art will understand that various specific parameters in the above embodiments can be changed without departing from the spirit of the present invention, and a plurality of specific embodiments are formed, which are common variation ranges of the present invention, and will not be described in detail herein.
Claims (10)
1. The ruthenium-based carrier type hydrogenation catalyst is characterized by comprising an active component, a carrier, a first auxiliary agent and a second auxiliary agent, wherein the active component is ruthenium salt, the carrier is zirconium oxide, the first auxiliary agent is zinc salt, the second auxiliary agent is molybdenum salt, and the first auxiliary agent accounts for 0.85-2.55% of the catalyst and the second auxiliary agent accounts for 0.017-0.085% of the catalyst in percentage by mass.
2. The ruthenium-based supported hydrogenation catalyst according to claim 1, wherein the ruthenium salt is present in an amount of 14 to 16% by mass based on the weight of the catalyst.
3. The ruthenium-based supported hydrogenation catalyst according to claim 1, wherein the zirconia is 82 to 85% by mass based on the weight of the catalyst.
4. The ruthenium-based supported hydrogenation catalyst according to claim 1, wherein the ruthenium salt is ruthenium chloride, the zinc salt is zinc sulfate, and the molybdenum salt is sodium molybdate.
5. A preparation method of a ruthenium-based carrier hydrogenation catalyst solution is characterized by comprising the following steps:
1) adding ruthenium salt, zinc salt, molybdenum salt and a zirconia carrier into water to prepare a metal salt solution;
2) adjusting the pH of the metal salt solution by using an alkali liquor to ensure that the pH of the metal salt solution is not less than 10; stirring simultaneously to carry out precipitation reaction;
3) after the precipitation reaction is finished, the reaction solution is contacted with hydrogen to carry out reduction reaction;
4) and after the reduction reaction is finished, cooling and washing the reaction solution to obtain the ruthenium-based carrier type hydrogenation catalyst aqueous solution.
6. The method for preparing a ruthenium-based supported hydrogenation catalyst solution according to claim 5, wherein in step 1), ruthenium salt, zinc salt, molybdenum salt and zirconia support and water are mixed in a mass ratio of 1: 6.
7. The method for preparing a ruthenium-based supported hydrogenation catalyst solution according to claim 5, wherein in the step 2), the precipitation reaction temperature is 50 to 80 ℃, and the precipitation reaction time is 1 to 2 hours; the mass ratio of the metal salt solution to the alkali liquor is 1: 0.6 to 1.2; the alkali liquor is a sodium hydroxide aqueous solution, and the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 10-15%.
8. The method for preparing a ruthenium-based supported hydrogenation catalyst solution according to claim 5, wherein in the step 3), the reduction reaction is carried out at a reaction temperature of 110 to 160 ℃ for 10 to 15 hours and under a hydrogen pressure of 3 to 5 MPa.
9. The method for preparing a ruthenium-based supported hydrogenation catalyst solution according to claim 5, wherein in step 4), the reaction solution is cooled to not more than 80 ℃, and the reaction solution is washed with water until the pH value is 7 to 8.
10. Use of a ruthenium-based supported hydrogenation catalyst according to claim 1 for the preparation of cyclohexene by partial hydrogenation of benzene.
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Cited By (2)
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| CN116651448A (en) * | 2023-05-22 | 2023-08-29 | 平顶山市拓青科技有限公司 | Ruthenium-based carrier type hydrogenation catalyst and preparation method of catalyst aqueous solution |
| CN116651448B (en) * | 2023-05-22 | 2024-06-25 | 平顶山市拓青科技有限公司 | Ruthenium-based carrier type hydrogenation catalyst and preparation method of catalyst aqueous solution |
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| CN116651448A (en) * | 2023-05-22 | 2023-08-29 | 平顶山市拓青科技有限公司 | Ruthenium-based carrier type hydrogenation catalyst and preparation method of catalyst aqueous solution |
| CN116651448B (en) * | 2023-05-22 | 2024-06-25 | 平顶山市拓青科技有限公司 | Ruthenium-based carrier type hydrogenation catalyst and preparation method of catalyst aqueous solution |
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