CN113042043A - Ruthenium-based hydrogenation catalyst, aqueous solution of ruthenium-based hydrogenation catalyst, and preparation method and application of aqueous solution - Google Patents
Ruthenium-based hydrogenation catalyst, aqueous solution of ruthenium-based hydrogenation catalyst, and preparation method and application of aqueous solution Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 91
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 83
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 147
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 claims abstract description 65
- 239000002184 metal Substances 0.000 claims abstract description 65
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 19
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 239000012266 salt solution Substances 0.000 claims description 34
- 238000006722 reduction reaction Methods 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 238000001556 precipitation Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- 229960001763 zinc sulfate Drugs 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical group Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 6
- 150000002503 iridium Chemical class 0.000 claims description 4
- 150000003057 platinum Chemical class 0.000 claims description 4
- 150000003303 ruthenium Chemical class 0.000 claims description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical group Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 description 35
- 239000012295 chemical reaction liquid Substances 0.000 description 30
- 238000011156 evaluation Methods 0.000 description 24
- 230000008859 change Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C5/11—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/60—Platinum group metals with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of cyclohexene preparation by benzene hydrogenation, in particular to a ruthenium-based hydrogenation catalyst, a ruthenium-based hydrogenation catalyst aqueous solution, a preparation method and an application. The ruthenium-based hydrogenation catalyst provided by the invention comprises an active component, a first auxiliary agent and a second auxiliary agent, wherein the active component is ruthenium, the first auxiliary agent is zinc, the second auxiliary agent is platinum and/or iridium, and the first auxiliary agent accounts for 5-15% of the catalyst and the second auxiliary agent accounts for 0.01-0.03% of the catalyst in percentage by mass. The ruthenium-based hydrogenation catalyst provided by the invention has the advantages that the metal ruthenium is used as an active component, the metal zinc is used as a first auxiliary agent, the metal platinum and/or iridium is used as a second auxiliary agent, and the metal ruthenium, the metal zinc and/or the metal iridium are matched with each other, so that the catalytic activity of the catalyst can be effectively improved, and the higher benzene conversion rate and the cyclohexene selectivity are realized.
Description
Technical Field
The invention relates to the field of cyclohexene preparation by benzene hydrogenation, in particular to a ruthenium-based hydrogenation catalyst, a ruthenium-based hydrogenation catalyst aqueous solution, a preparation method and an application.
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 carrier type catalysts which have poor stability, and in the production and use processes, the carrier is easy to separate from active metals, so that catalyst pulverization is caused, the reaction conversion rate and selectivity are reduced sharply, and the pulverized catalyst floats and is easy to run off; secondly, the carrier catalyst has less active metal ruthenium and poor unit catalyst activity, a large amount of carrier type catalyst must be added in order to achieve the same productivity in the production, so that the concentration of reaction slurry is larger, the replacement period of the catalyst is short, the regeneration is difficult, the same regeneration effect is achieved compared with the metal catalyst, and the regeneration amount of the carrier type catalyst is about five times that of the metal catalyst; finally, although the carrier type catalyst can realize higher benzene conversion rate and cyclohexene selectivity to a certain extent, the improvement range of the conventional catalyst on the benzene conversion rate and the cyclohexene selectivity is still limited, and the catalytic activity of the catalyst is not high, so that the industrial production is greatly limited.
Disclosure of Invention
The invention aims to overcome the defects that the existing catalyst for preparing cyclohexene by benzene hydrogenation has limited improvement range of benzene conversion rate and cyclohexene selectivity, low catalytic activity, large usage amount and difficult regeneration, and further provides a ruthenium-based hydrogenation catalyst, a ruthenium-based hydrogenation catalyst aqueous solution, a preparation method and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
the ruthenium-based hydrogenation catalyst comprises an active component, a first auxiliary agent and a second auxiliary agent, wherein the active component is ruthenium, the first auxiliary agent is zinc, the second auxiliary agent is platinum and/or iridium, and the first auxiliary agent accounts for 5-15% of the catalyst and the second auxiliary agent accounts for 0.01-0.03% of the catalyst in percentage by mass.
Preferably, the active component accounts for 84-94% of the catalyst by mass percent.
Preferably, the second auxiliary agent is platinum and iridium, and the mass ratio of platinum to iridium is 1: (0.8-1.2).
The invention also provides a ruthenium-based hydrogenation catalyst aqueous solution, wherein the catalyst in the ruthenium-based hydrogenation catalyst aqueous solution is the catalyst, and the mass content of the catalyst in the ruthenium-based hydrogenation catalyst aqueous solution is not more than 10%.
The invention also provides a preparation method of the ruthenium-based hydrogenation catalyst aqueous solution, which comprises the following steps:
1) adding ruthenium salt, zinc salt, platinum salt and/or iridium salt into water to prepare a metal salt solution;
2) adding alkali liquor into the metal salt solution, controlling the pH value of the mixed solution to be more than 10, and stirring to perform a 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 hydrogenation catalyst aqueous solution.
Preferably, the mass fraction of the metal ruthenium, the mass fraction of the metal zinc and the mass fraction of the metal platinum and/or the metal iridium in the metal salt solution are respectively 1-5%, 0.4-0.7% and 0.001-0.003%.
Preferably, the ruthenium salt is ruthenium chloride, the zinc salt is zinc sulfate, the platinum salt is platinum chloride, and the iridium salt is iridium chloride.
Preferably, the mass ratio of the metal salt solution to the alkali liquor is 1: (0.6-1.2);
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, the precipitation reaction temperature in the step 2) is 20-30 ℃, and the precipitation reaction time is 1-2 h;
in the step 3), the reduction reaction temperature is 120-150 ℃, the reduction reaction time is 8-12h, and the hydrogen pressure is 2-5 MPa.
Preferably, in step 4), the temperature of the reaction solution is reduced to below 80 ℃, and the reaction solution is washed by water until the pH value of the reaction solution is 7-8.
The invention also provides an application of the ruthenium-based hydrogenation catalyst, the ruthenium-based hydrogenation catalyst aqueous solution or the ruthenium-based hydrogenation catalyst aqueous solution prepared by the preparation method in preparation of cyclohexene by partial hydrogenation of benzene.
The invention has the beneficial effects that:
1. according to the invention, in the process of preparing cyclohexene by benzene hydrogenation, the ruthenium-based hydrogenation catalyst is prepared by using metal ruthenium as an active component, metal zinc as a first auxiliary agent, and metal platinum and/or iridium as a second auxiliary agent, which are matched with each other, so that the catalytic activity of the catalyst can be effectively improved, and each gram of catalyst can convert up to 180 grams of benzene within 1 hour, which is far higher than the average level of 110 grams of benzene at present in China, and simultaneously, higher benzene conversion rate and cyclohexene selectivity are realized, and the benzene conversion rate is greatly improved on the premise of maintaining the high cyclohexene selectivity.
In addition, the ruthenium-based hydrogenation catalyst has long service life and stronger anti-poisoning capability, and compared with an amorphous 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 carrier type catalyst, the catalyst has simple regeneration steps and is easy to realize industrialization.
2. The ruthenium-based hydrogenation catalyst provided by the invention is characterized in that the second auxiliary agent is platinum and iridium, and the mass ratio of the platinum to the iridium is 1: (0.8-1.2). According to the invention, the platinum and the iridium in a specific ratio are used as the second auxiliary agent, and the specific active component and the first auxiliary agent are matched, so that the catalytic activity of the catalyst can be further improved, and the higher benzene conversion rate and the cyclohexene selectivity can be maintained.
3. The preparation method of the aqueous solution of the ruthenium-based 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 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 noncrystalline 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
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing the change of benzene conversion with time in the catalyst activity evaluation result graph of example 1 of the present invention;
FIG. 2 is a graph showing the variation of cyclohexene selectivity to benzene conversion in the catalyst activity evaluation result of example 1 of the present invention;
FIG. 3 is a graph showing the change of benzene conversion with time in the catalyst activity evaluation result chart of example 2 of the present invention;
FIG. 4 is a graph showing a change in cyclohexene selectivity versus benzene conversion in a catalyst activity evaluation result graph according to example 2 of the present invention;
FIG. 5 is a graph showing the change of benzene conversion with time in the catalyst activity evaluation result chart of example 3 of the present invention;
FIG. 6 is a graph showing the variation of cyclohexene selectivity versus benzene conversion in the catalyst activity evaluation result of example 3 of the present invention;
FIG. 7 is a graph showing the change of benzene conversion with time in the catalyst activity evaluation result chart of example 4 of the present invention;
FIG. 8 is a graph showing the variation of cyclohexene selectivity versus benzene conversion in the catalyst activity evaluation result of example 4 of the present invention;
FIG. 9 is a graph showing the change of benzene conversion with time in the catalyst activity evaluation result chart of example 5 of the present invention;
FIG. 10 is a graph showing the variation of cyclohexene selectivity versus benzene conversion in the catalyst activity evaluation result of example 5 of the present invention;
FIG. 11 is a graph showing the change of benzene conversion with time in the catalyst activity evaluation result chart of comparative example 1 of the present invention;
FIG. 12 is a graph showing the change in cyclohexene selectivity versus benzene conversion in the catalyst activity evaluation result of comparative example 1 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example provides an aqueous solution of ruthenium-based hydrogenation catalyst, comprising, as active ingredients, 4.5g of ruthenium, 0.43g of zinc as a first promoter, and 0.001g of platinum as a second promoter;
the preparation method of the ruthenium-based hydrogenation catalyst aqueous solution comprises the following steps:
1) adding ruthenium chloride, zinc sulfate and platinum chloride into water at room temperature to prepare a metal salt solution, wherein the mass fraction of metal ruthenium in the metal salt solution is 4.5%, the mass fraction of metal zinc is 0.43%, and the mass fraction of metal platinum is 0.001%;
2) adding 100g of the metal salt solution into a reaction kettle, then adding 100g of a sodium hydroxide aqueous solution (the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 10%) into the metal salt solution, controlling the pH value of the mixed solution to be 11, and stirring to perform a precipitation reaction at the temperature of 25 ℃ for 1 h;
3) introducing hydrogen into the reaction kettle after the precipitation reaction is finished so that the reaction liquid is in contact with the hydrogen to carry out reduction reaction, wherein the reduction reaction temperature is 145 ℃, the reduction reaction time is 10 hours, and the hydrogen pressure is 3.5 MPa;
4) after the reduction reaction is finished, cooling the reaction liquid to 75 ℃, then discharging the cooled reaction liquid from the reaction kettle, and then washing the reaction liquid with high-purity water until the pH value of the reaction liquid is 7.1 to obtain the aqueous solution of the ruthenium-based hydrogenation catalyst, wherein the mass content of the catalyst in the aqueous solution of the ruthenium-based hydrogenation catalyst is 8%.
The ruthenium-based hydrogenation catalysts prepared in the above examples were evaluated for their catalytic performance by the following methods:
1. benzene conversion and cyclohexene selectivity:
firstly, weighing and calculating the mass of a catalyst in 5g of ruthenium-based hydrogenation catalyst aqueous solution, then putting the catalyst, 50 g of zinc sulfate, 10 g of zirconium oxide and 280 ml of water into an autoclave, processing the mixture for 22 hours at 145 ℃ under the rotating speed of 1000 r/min and the hydrogen pressure of 5.0MPa, adjusting the stirring rotating speed to 1600 r/min, adding 140ml of thiophene-free benzene through a high-pressure tank, starting timing sampling, analyzing oil phase components by gas chromatography, and calculating the benzene conversion rate and the cyclohexene selectivity.
2. And (3) making a data curve of the benzene conversion rate and the cyclohexene selectivity according to the relationship between the time and the benzene conversion rate and the cyclohexene selectivity, and reading the cyclohexene selectivity at different benzene conversion rates.
3. Method for obtaining γ (catalytic activity): the γ value is obtained by the following calculation formula.
In the above formula:
γ: catalyst activity, benzene conversion/g;
v: benzene loading, 140 mL;
ρ: benzene density, 0.88 g/mL;
ω: benzene conversion,%;
t: reaction time to achieve conversion;
DH: 5g mass of catalyst/g in aqueous ruthenium-based hydrogenation catalyst solution.
The catalyst activity evaluation results are shown in fig. 1, fig. 2 and table 1.
Table 1 example 1 evaluation results of catalyst activity
| Reaction time (min) | 8.5 | 11.0 | 13.5 | 17.0 |
| Benzene conversion (%) | 40 | 50 | 60 | 70 |
| Cyclohexene selectivity (%) | 87.5 | 85.7 | 83.5 | 80.0 |
| Catalyst Activity gamma/g | 177.5 | 171.4 | 167.6 | 155.3 |
Example 2
This example provides an aqueous solution of ruthenium-based hydrogenation catalyst, comprising 3.8g of ruthenium as an active component, 0.48g of zinc as a first promoter, and 0.001g of platinum as a second promoter;
the preparation method of the ruthenium-based hydrogenation catalyst aqueous solution comprises the following steps:
1) adding 8.62g of ruthenium chloride, 1.185g of zinc sulfate and 0.0017g of platinum chloride into 90.19g of water at room temperature to prepare a metal salt solution, wherein the mass fraction of the ruthenium metal, the mass fraction of the zinc metal and the mass fraction of the platinum metal in the metal salt solution are respectively 3.8%, 0.48% and 0.001%, respectively;
2) adding the metal salt solution into a reaction kettle, then adding 85g of sodium hydroxide aqueous solution (the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 12%) into the metal salt solution, controlling the pH value of the mixed solution to be 11, stirring to perform a precipitation reaction, wherein the precipitation reaction temperature is 30 ℃, and the precipitation reaction time is 1.2 h;
3) introducing hydrogen into the reaction kettle after the precipitation reaction is finished so that the reaction liquid is in contact with the hydrogen to carry out reduction reaction, wherein the reduction reaction temperature is 135 ℃, the reduction reaction time is 11h, and the hydrogen pressure is 4.5 MPa;
4) after the reduction reaction is finished, cooling the reaction liquid to 75 ℃, then discharging the cooled reaction liquid from the reaction kettle, and then washing the reaction liquid with high-purity water until the pH value of the reaction liquid is 7.2 to obtain the aqueous solution of the ruthenium-based hydrogenation catalyst, wherein the mass content of the catalyst in the aqueous solution of the ruthenium-based hydrogenation catalyst is 8%.
The ruthenium-based hydrogenation catalysts prepared in the above examples were evaluated for their catalytic performance in the same manner as in example 1, and the results of the evaluation of catalyst activity are shown in fig. 3, 4 and table 2.
Table 2 example 2 evaluation results of catalyst activity
| Reaction time (min) | 8.9 | 11.5 | 14.0 | 17.5 |
| Benzene conversion (%) | 40 | 50 | 60 | 70 |
| Cyclohexene selectivity (%) | 86.7 | 85.0 | 82.1 | 78.1 |
| Catalyst Activity gamma/g | 169.5 | 164.0 | 160.5 | 150.9 |
Example 3
This example provides an aqueous solution of ruthenium-based hydrogenation catalyst, which comprises 4.2g of active component ruthenium, 0.4g of first auxiliary zinc, and 0.0014g of second auxiliary platinum;
the preparation method of the ruthenium-based hydrogenation catalyst aqueous solution comprises the following steps:
1) adding ruthenium chloride, zinc sulfate and platinum chloride into water at room temperature to prepare a metal salt solution, wherein the mass fraction of metal ruthenium in the metal salt solution is 4.2%, the mass fraction of metal zinc is 0.4%, and the mass fraction of metal platinum is 0.0014%;
2) adding 100g of the metal salt solution into a reaction kettle, then adding 100g of a sodium hydroxide aqueous solution (the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 10%) into the metal salt solution, controlling the pH value of the mixed solution to be 10, and stirring to perform a precipitation reaction at the temperature of 25 ℃ for 1 h;
3) introducing hydrogen into the reaction kettle after the precipitation reaction is finished so that the reaction liquid is in contact with the hydrogen to carry out reduction reaction, wherein the reduction reaction temperature is 140 ℃, the reduction reaction time is 10 hours, and the hydrogen pressure is 4 MPa;
4) after the reduction reaction is finished, cooling the reaction liquid to 75 ℃, then discharging the cooled reaction liquid from the reaction kettle, and then washing the reaction liquid with high-purity water until the pH value of the reaction liquid is 7.1 to obtain the aqueous solution of the ruthenium-based hydrogenation catalyst, wherein the mass content of the catalyst in the aqueous solution of the ruthenium-based hydrogenation catalyst is 8%.
The ruthenium-based hydrogenation catalysts prepared in the above examples were evaluated for their catalytic performance in the same manner as in example 1, and the results of the evaluation of catalyst activity are shown in fig. 5, 6 and table 3.
Table 3 example 3 catalyst activity evaluation results
| Reaction time (min) | 8.5 | 11.0 | 14.5 | 18.2 |
| Benzene conversion (%) | 40 | 50 | 60 | 70 |
| Cyclohexene selectivity (%) | 86.3 | 84.1 | 81.1 | 75.6 |
| Catalyst Activity gamma/g | 178.5 | 171.6 | 156.1 | 145.1 |
Example 4
This example provides an aqueous solution of ruthenium-based hydrogenation catalyst, comprising 4.5g of ruthenium as an active component, 0.43g of zinc as a first promoter, and 0.001g of iridium as a second promoter;
the preparation method of the ruthenium-based hydrogenation catalyst aqueous solution comprises the following steps:
1) adding ruthenium chloride, zinc sulfate and iridium chloride into water at room temperature to prepare a metal salt solution, wherein the mass fraction of the ruthenium metal in the metal salt solution is 4.5%, the mass fraction of the zinc metal in the metal salt solution is 0.43%, and the mass fraction of the iridium metal in the metal salt solution is 0.001%;
2) adding 100g of the metal salt solution into a reaction kettle, then adding 100g of a sodium hydroxide aqueous solution (the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 10%) into the metal salt solution, controlling the pH value of the mixed solution to be 11, and stirring to perform a precipitation reaction at the temperature of 25 ℃ for 1 h;
3) introducing hydrogen into the reaction kettle after the precipitation reaction is finished so that the reaction liquid is in contact with the hydrogen to carry out reduction reaction, wherein the reduction reaction temperature is 145 ℃, the reduction reaction time is 10 hours, and the hydrogen pressure is 3.5 MPa;
4) after the reduction reaction is finished, cooling the reaction liquid to 75 ℃, then discharging the cooled reaction liquid from the reaction kettle, and then washing the reaction liquid with high-purity water until the pH value of the reaction liquid is 7.1 to obtain the aqueous solution of the ruthenium-based hydrogenation catalyst, wherein the mass content of the catalyst in the aqueous solution of the ruthenium-based hydrogenation catalyst is 8%.
The ruthenium-based hydrogenation catalysts prepared in the above examples were evaluated for their catalytic performance in the same manner as in example 1, and the results of the evaluation of catalyst activity are shown in fig. 7, fig. 8 and table 4.
Table 4 example 4 catalyst activity evaluation results
| Reaction time (min) | 11.0 | 14.0 | 17.5 | 22.0 |
| Benzene conversion (%) | 40 | 50 | 60 | 70 |
| Cyclohexene selectivity (%) | 87.7 | 85.8 | 83.3 | 80.2 |
| Catalyst Activity gamma/g | 137.1 | 134.7 | 129.3 | 120.0 |
Example 5
This example provides an aqueous ruthenium-based hydrogenation catalyst solution comprising, as active ingredients, 4.5g of ruthenium, 0.43g of zinc as a first promoter, 0.0005g of iridium metal and 0.0005g of platinum metal as a second promoter;
the preparation method of the ruthenium-based hydrogenation catalyst aqueous solution comprises the following steps:
1) adding ruthenium chloride, zinc sulfate, platinum chloride and iridium chloride into water at room temperature to prepare a metal salt solution, wherein the mass fraction of the ruthenium metal in the metal salt solution is 4.5%, the mass fraction of the zinc metal is 0.43%, the mass fraction of the iridium metal is 0.0005%, and the mass fraction of the platinum metal is 0.0005%;
2) adding 100g of the metal salt solution into a reaction kettle, then adding 100g of a sodium hydroxide aqueous solution (the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 10%) into the metal salt solution, controlling the pH value of the mixed solution to be 11, and stirring to perform a precipitation reaction at the temperature of 25 ℃ for 1 h;
3) introducing hydrogen into the reaction kettle after the precipitation reaction is finished so that the reaction liquid is in contact with the hydrogen to carry out reduction reaction, wherein the reduction reaction temperature is 145 ℃, the reduction reaction time is 10 hours, and the hydrogen pressure is 3.5 MPa;
4) after the reduction reaction is finished, cooling the reaction liquid to 75 ℃, then discharging the cooled reaction liquid from the reaction kettle, and then washing the reaction liquid with high-purity water until the pH value of the reaction liquid is 7.1 to obtain the aqueous solution of the ruthenium-based hydrogenation catalyst, wherein the mass content of the catalyst in the aqueous solution of the ruthenium-based hydrogenation catalyst is 8%.
The ruthenium-based hydrogenation catalysts prepared in the above examples were evaluated for their catalytic performance in the same manner as in example 1, and the results of the evaluation of catalyst activity are shown in fig. 9, 10 and table 5.
Table 5 example 5 evaluation results of catalyst activity
| Reaction time (min) | 8.3 | 10.8 | 13.4 | 16.4 |
| Benzene conversion (%) | 40 | 50 | 60 | 70 |
| Cyclohexene selectivity (%) | 87.5 | 85.4 | 83.0 | 80.4 |
| Catalyst Activity gamma/g | 181.8 | 174.6 | 168.9 | 161.0 |
Comparative example 1
The comparative example provides an aqueous solution of a ruthenium-based hydrogenation catalyst comprising, as an active component, 4.5g of ruthenium, and 0.43g of a first auxiliary agent of zinc;
the preparation method of the ruthenium-based hydrogenation catalyst aqueous solution comprises the following steps:
1) adding ruthenium chloride and zinc sulfate into water at room temperature to prepare a metal salt solution, wherein the mass fraction of metal ruthenium in the metal salt solution is 4.5%, and the mass fraction of metal zinc is 0.43%;
2) adding 100g of the metal salt solution into a reaction kettle, then adding 100g of a sodium hydroxide aqueous solution (the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution is 10%) into the metal salt solution, controlling the pH value of the mixed solution to be 11, and stirring to perform a precipitation reaction at the temperature of 25 ℃ for 1 h;
3) introducing hydrogen into the reaction kettle after the precipitation reaction is finished so that the reaction liquid is in contact with the hydrogen to carry out reduction reaction, wherein the reduction reaction temperature is 145 ℃, the reduction reaction time is 10 hours, and the hydrogen pressure is 3.5 MPa;
4) after the reduction reaction is finished, cooling the reaction liquid to 75 ℃, then discharging the cooled reaction liquid from the reaction kettle, and then washing the reaction liquid with high-purity water until the pH value of the reaction liquid is 7.1 to obtain the aqueous solution of the ruthenium-based hydrogenation catalyst, wherein the mass content of the catalyst in the aqueous solution of the ruthenium-based hydrogenation catalyst is 8%.
The ruthenium-based hydrogenation catalysts prepared in the above comparative examples were evaluated for their catalytic performance in the same manner as in example 1, and the results of the evaluation of catalyst activity are shown in table 6, fig. 11 and fig. 12.
Table 6 evaluation results of catalyst activity of comparative example 1
| Reaction time (min) | 12.3 | 15.1 | 19.0 | 23.3 |
| Benzene conversion (%) | 40 | 50 | 60 | 70 |
| Cyclohexene selectivity (%) | 87.2 | 85.3 | 83.0 | 80.0 |
| Catalyst Activity gamma/g | 122.6 | 124.1 | 119.1 | 113.3 |
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The ruthenium-based hydrogenation catalyst is characterized by comprising an active component, a first auxiliary agent and a second auxiliary agent, wherein the active component is ruthenium, the first auxiliary agent is zinc, the second auxiliary agent is platinum and/or iridium, and the first auxiliary agent accounts for 5-15% of the catalyst and the second auxiliary agent accounts for 0.01-0.03% of the catalyst in percentage by mass.
2. The ruthenium-based hydrogenation catalyst according to claim 1, wherein the second promoter is platinum and iridium, and the mass ratio of platinum to iridium is 1: (0.8-1.2).
3. An aqueous ruthenium-based hydrogenation catalyst solution, wherein the catalyst in the aqueous ruthenium-based hydrogenation catalyst solution is the catalyst according to claim 1 or 2, and the mass content of the catalyst in the aqueous ruthenium-based hydrogenation catalyst solution is not more than 10%.
4. A method for preparing an aqueous ruthenium-based hydrogenation catalyst according to claim 3, comprising the steps of:
1) adding ruthenium salt, zinc salt, platinum salt and/or iridium salt into water to prepare a metal salt solution;
2) adding alkali liquor into the metal salt solution, controlling the pH value of the mixed solution to be more than 10, and stirring to perform a 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 hydrogenation catalyst aqueous solution.
5. The method for preparing an aqueous ruthenium-based hydrogenation catalyst solution according to claim 4, wherein the metal salt solution contains 1 to 5 mass% of metallic ruthenium, 0.4 to 0.7 mass% of metallic zinc, and 0.001 to 0.003 mass% of metallic platinum and/or metallic iridium.
6. The method of preparing an aqueous ruthenium-based hydrogenation catalyst solution according to claim 4 or 5, wherein the ruthenium salt is ruthenium chloride, the zinc salt is zinc sulfate, the platinum salt is platinum chloride, and the iridium salt is iridium chloride.
7. The method for preparing an aqueous ruthenium-based hydrogenation catalyst according to any one of claims 4 to 6, wherein the mass ratio of the metal salt solution to the alkali solution is 1: (0.6-1.2);
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 an aqueous ruthenium-based hydrogenation catalyst according to any one of claims 4 to 7, wherein the precipitation reaction temperature in step 2) is 20 ℃ to 30 ℃ and the precipitation reaction time is 1h to 2 h;
in the step 3), the reduction reaction temperature is 120-150 ℃, the reduction reaction time is 8-12h, and the hydrogen pressure is 2-5 MPa.
9. The method for preparing an aqueous ruthenium-based hydrogenation catalyst according to any one of claims 4 to 8, wherein the temperature of the reaction solution in step 4) is lowered to 80 ℃ or lower, and the reaction solution is washed with water until the pH of the reaction solution is 7 to 8.
10. Use of the ruthenium-based hydrogenation catalyst according to claim 1 or 2, the aqueous ruthenium-based hydrogenation catalyst solution according to claim 3 or the aqueous ruthenium-based hydrogenation catalyst solution prepared by the preparation process according to any one of claims 4 to 9 for the partial hydrogenation of benzene to cyclohexene.
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