CN115430422A - Preparation method of spherical twin crystal ruthenium catalyst, catalyst prepared by preparation method, and method for preparing cyclohexene by using catalyst - Google Patents
Preparation method of spherical twin crystal ruthenium catalyst, catalyst prepared by preparation method, and method for preparing cyclohexene by using catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000013078 crystal Substances 0.000 title claims abstract description 30
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- OSKSAMGBRKRQOZ-UHFFFAOYSA-N benzene cyclohexene Chemical compound C1CCC=CC1.C1CCC=CC1.C1=CC=CC=C1 OSKSAMGBRKRQOZ-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229920001778 nylon Polymers 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
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate 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
-
- B01J35/40—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- 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
Abstract
The invention relates to a preparation method of a spherical twin crystal ruthenium catalyst, a catalyst prepared by the spherical twin crystal ruthenium catalyst, and a method for preparing cyclohexene by using the catalyst. The preparation method of the catalyst disclosed by the invention is simple, few in steps and high in repeatability; the cyclohexene preparation process has good activity performance and long one-way service life, and can greatly improve the economic benefit of the whole process.
Description
Technical Field
The present disclosure belongs to the technical field of catalytic science and chemical industry. Specifically, the present disclosure relates to a method for preparing a twin ruthenium catalyst, a catalyst prepared therefrom, and a method for preparing cyclohexene using the same, and more particularly, to a method for preparing a spherical twin ruthenium catalyst, a catalyst prepared therefrom, and a method for preparing cyclohexene by selective hydrogenation of benzene using the same.
Background
Cyclohexene as an important organic chemical raw material is widely used for production of fine chemicals such as medicines, lysine feed additives, nylon, polyester and the like. Particularly, cyclohexene is used as a raw material to produce cyclohexanol in a hydration mode, further cyclohexanone and adipic acid are produced, and finally nylon-6 and nylon-66 are obtained through polymerization, so that the production process of nylon-6 and nylon-66 is greatly simplified. In the production of nylon-6 and nylon-66, the process route for synthesizing nylon-6 and nylon-66 by using cyclohexene as a raw material has the characteristics of safety, energy conservation, high economic benefit and environmental friendliness. Thermodynamically, however, cyclohexane is more easily formed by the hydrogenation of benzene. Therefore, the development of a catalyst with stable performance and high conversion rate and high cyclohexene selectivity is the key of the technology.
Currently, ru-Zn nano-catalyst is mainly adopted for benzene selective hydrogenation in industry. The problems that exist are mainly: 1. the activity is low: when the benzene conversion rate is 40%, the selectivity of the cyclohexene is about 80%; 2. the structural stability is poor: after the catalyst is operated for a period of time, the particle size of the catalyst is obviously increased, and the activity and the selectivity are reduced; 3. the preparation process is complex and is finished by steps of precipitation, reduction and the like. Therefore, much work has been done to optimize the catalyst preparation process and improve the catalyst performance.
At present, the research on the nano ruthenium catalyst mainly focuses on the aspects of auxiliary agent modification, active site regulation and control of metal ruthenium, carrier regulation and the like. With little attention paid to the morphology of the catalyst.
The catalytic performance and stability of the nano-catalyst have a great relationship with the morphology of the catalyst. The spherical twin catalyst has a large amount of lattice defects and lattice stress, so that the spherical twin catalyst has more excellent performance. The spherical twin catalyst particles have smaller contact area, so better dispersity can be maintained. This makes it less prone to austenite ripening and agglomeration during the reaction, resulting in a longer service life.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing a spherical twin crystal Ru-M (M = Mo, co, fe, la, ce, zn and the like) catalyst by a one-step hydrothermal method and application of the prepared catalyst in preparation of cyclohexene by selective hydrogenation of benzene. The catalyst consists of an active component Ru and an auxiliary agent M, wherein M is any one of Mo, co, fe, la, ce and Zn; wherein, the atomic number ratio of the active component metal Ru and the auxiliary agent M is that Ru is 1, and M is 0.01-0.2.
Accordingly, it is an object of the present disclosure to provide a method for preparing a spherical twin ruthenium catalyst.
It is another object of the present disclosure to provide a spherical twin ruthenium catalyst prepared using the above method.
It is still another object of the present disclosure to provide a method for preparing cyclohexene using the spherical twin crystal ruthenium catalyst.
According to one aspect of the present disclosure, there is provided a method for preparing a spherical twin ruthenium catalyst, comprising the steps of:
1) At normal temperature, precursor of active ingredient Ru, precursor of auxiliary agent M, reducing agent, crystal directing agent and surfactant are ultrasonically dissolved in water to make Ru 3+ The ion content is 0.02-0.20 mol/L; the atomic number ratio of each component in the catalyst is that Ru is 1, M is 0.01-0.2; and adjusting the pH =8-10 with an alkali solution,
2) Transferring the fully dissolved solution in the step 1) to a polytetrafluoroethylene kettle with rough and hydrophobic inner wall;
3) Sealing the polytetrafluoroethylene kettle in the step 2), and reacting in a homogeneous reactor at 100-200 ℃ for 1-10 hours to obtain a crystallization reaction mixture;
4) Washing the crystallization reaction mixture in step 3) with deionized water to neutrality and free of Cl - And (7) detecting. To obtain the spherical twin crystal ruthenium catalyst,
wherein the precursor of Ru in the step 1) is ruthenium chloride,
the precursor of the auxiliary M is any one of acetate, sulfate or nitrate of M and other organic or inorganic salts, wherein M is any one of Mo, co, fe, la, ce and Zn,
the reducing agent is at least one selected from formaldehyde, isopropanol and ethylene glycol,
the crystal guiding agent is at least one of KBr, KCl and KI,
the surfactant is at least one selected from cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and sodium polyacrylate,
the alkali solution is NaOH or KOH aqueous solution, and the mass fraction is 3-20%.
According to another aspect of the present disclosure, there is provided a spherical twin ruthenium catalyst prepared using the above method.
According to another aspect of the present disclosure, there is provided a method for preparing cyclohexene using the spherical twin ruthenium catalyst, the method including:
hydrogenating benzene in the presence of the spherical twin crystal ruthenium catalyst to produce cyclohexene.
Advantageous effects
The catalyst nanocrystal particles prepared by the method of the present invention are spherical twins that approximate a sphere (referred to herein as spherical twins). The spherical twin catalyst has a large amount of lattice defects and lattice stress, so that the spherical twin catalyst has more excellent performance. The spherical twin catalyst nano crystal grains have smaller contact area, so better dispersity can be maintained. The austenite is not easy to mature and agglomerate in the reaction process, so that the service life is longer; meanwhile, the contact area between the catalyst and the reactant is not affected, so that the catalytic performance of the catalyst is not affected. The conversion selectivity of the current industrial catalyst is respectively 40% and 80% and the stability of the catalyst is not good, while the conversion rate and the selectivity of the catalyst of the patent respectively reach 53.5% and 83.3%. After the industrial catalyst is mechanically applied to a laboratory evaluation device for 10 times, the particle size of the catalyst is increased by 15 percent. The particle size of the catalyst of the patent is increased by 3-5%. After the catalyst is mechanically used for 10 times, the conversion rate and the selectivity of the catalyst still reach 52.9 percent and 83.7 percent respectively
The preparation method of the catalyst disclosed by the invention is simple, few in steps and high in repeatability; the cyclohexene preparation process has good activity performance and long one-way service life, and can greatly improve the economic benefit of the whole process.
Drawings
Fig. 1 is a schematic representation of the morphology of the catalyst of the invention (TEM picture).
Fig. 2 is a schematic of the morphology of a commercial catalyst sample of a comparative example (TEM picture).
Detailed Description
The invention will be further described by means of specific examples. It will be understood that the scope of the invention is not limited to these examples.
In the following examples, the raw materials used were purchased from Shanxi Kaida chemical company Limited, and from the national drug group chemical reagents company Limited, and the experimental instruments and equipment used were off-standard custom made by the Wailan chemical company.
According to an embodiment of the present disclosure, there is provided a method for preparing a spherical twin ruthenium catalyst, characterized by comprising the steps of:
1) At normal temperature, precursor of active ingredient Ru, precursor of auxiliary agent M, reducing agent, crystal directing agent and surfactant are ultrasonically dissolved in water to make Ru 3+ The ion is 0.02-0.20 mol/L; the atomic number ratio of each component in the solution is that Ru is 1, and M is 0.01-0.2; and adjusting the pH =8-10 with an alkali solution,
2) Transferring the fully dissolved solution in the step 1) to a polytetrafluoroethylene kettle;
3) Sealing the polytetrafluoroethylene kettle in the step 2), and reacting for 1-10 hours at 100-200 ℃ to obtain a crystallization reaction mixture;
4) Washing the crystallization reaction mixture in the step 3) to be neutral without Cl by using deionized water - And (7) detecting. To obtain the spherical twin crystal ruthenium catalyst,
wherein the precursor of Ru in the step 1) is ruthenium chloride,
the precursor of the auxiliary M is any one of acetate, sulfate or nitrate of M and other organic or inorganic salts, the M is any one of Mo, co, fe, la, ce and Zn,
the reducing agent is at least one selected from formaldehyde, isopropanol and ethylene glycol,
the crystal guiding agent is at least one selected from KBr, KCl and KI,
the surfactant is at least one selected from cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and sodium polyacrylate,
the alkali solution is NaOH or KOH aqueous solution, and the mass fraction is 3-20%.
In the present disclosure, the teflon reactor is a reactor whose inner wall is rough and hydrophobic, unlike an alloy reactor whose inner wall is smooth.
According to the method disclosed by the invention, a polytetrafluoroethylene kettle with a rough and hydrophobic inner wall is used, so that a large number of nucleation sites can be provided for a nanocrystal forming process, the supersaturation degree of a solution is reduced, the chemical potential of a system is reduced, and finally obtained nanocrystals are spherical twin crystals with low chemical potential, so that the service life is longer. Moreover, applicants have also surprisingly found that the twins can achieve higher benzene conversion and better stability while maintaining cyclohexene selectivity substantially unchanged.
According to one embodiment of the present disclosure, wherein,
the precursor of the auxiliary M is sulfate of M, wherein M is any one of Mo, co, fe and Zn;
according to one embodiment of the present disclosure, wherein,
the reducing agent is at least one selected from formaldehyde and isopropanol;
according to one embodiment of the present disclosure, wherein,
the crystal guiding agent is KBr;
according to one embodiment of the present disclosure, wherein,
the surfactant is at least one selected from cetyl trimethyl ammonium bromide and sodium polyacrylate;
according to one embodiment of the present disclosure, wherein,
the mass fraction of the alkali solution is 5-15%.
By using the specific reaction reagent and the reaction container, the spherical twin crystal nano catalyst with high activity and high stability can be obtained.
According to one embodiment of the present disclosure, wherein,
Ru 3+ the ion concentration is 0.02-0.20 mol/L; m concentration of Ru 3+ 0.01 to 0.2 times of the ion concentration; the concentration of the crystal directing agent is 1-10g/L; the concentration of the surfactant is 10-20g/L;
according to one embodiment of the present disclosure, wherein,
1) 7.95g of RuCl were added at 30 ℃ 3 ·3H 2 O, 0.2g of ZnSO 4 ·7H 2 Dissolving O, 2g of KBr and 4.7g of hexadecyl trimethyl ammonium bromide in 100ml of water by ultrasonic waves, adding 200ml of 37% formaldehyde solution, and adjusting the pH to be =9 by using 10% KOH aqueous solution;
2) Transferring the fully dissolved solution in the step 1) to a polytetrafluoroethylene kettle;
3) Sealing the polytetrafluoroethylene kettle in the step 2), and reacting in a homogeneous reactor at 170 ℃ for 8 hours to obtain a crystallization reaction mixture;
4) Washing the crystallization reaction mixture in the step 3) by deionized water until the mixture is neutral and free of Cl - And (7) detecting. Obtaining the spherical twin crystal ruthenium catalyst.
In the present disclosure, the polytetrafluoroethylene tank is a polytetrafluoroethylene tank having a rough inner wall that is hydrophobic.
According to one embodiment of the present disclosure, there is provided a spherical twin ruthenium catalyst prepared using the above method.
Catalysts prepared using the methods of the present disclosure have longer useful lives. Moreover, applicants have also surprisingly found that the catalyst thus prepared can achieve higher benzene conversion while maintaining cyclohexene selectivity substantially unchanged.
According to an embodiment of the present disclosure, there is provided a method for preparing cyclohexene using the spherical twin crystal ruthenium catalyst, including:
hydrogenating benzene in the presence of the spherical twin crystal ruthenium catalyst to produce cyclohexene.
When cyclohexene is prepared using the catalyst prepared by the process of the present disclosure, the catalyst has a longer service life. Moreover, applicants have also surprisingly found that higher benzene conversions can be achieved while maintaining cyclohexene selectivity substantially unchanged. And the conversion rate and the selectivity can be kept unchanged after multiple cycles.
Example 1
7.95g of RuCl were taken 3 ·3H 2 O (30.4 mmol), 0.2g of ZnSO 4 ·7H 2 O (0.7 mmol), 2g KBr, 4.7g hexadecyltrimethylammonium bromide were dissolved in 100ml of water by sonication, 200ml of a 37% formaldehyde solution were added, and the pH was adjusted with 10% KOH in water =9. And transferred to a 500ml teflon kettle. The autoclave was then placed in a homogeneous reactor and reacted at 170 ℃ for 8 hours. The obtained black precipitate is washed with deionized water for 4 times till no Cl - And (7) detecting. The resulting catalyst sample was dispersed in deionized water. The nanoparticle size was measured to be 4-6nm and the morphology was spherical as shown in FIG. 1.
Example 2
The catalyst was prepared according to the method of example 1. Except that the reaction time was 4 hours.
Example 3
The catalyst was prepared according to the method of example 1. Except that the amount of KBr added was 1g.
Example 4
The catalyst was prepared according to the method of example 1. Except that hexadecyltrimethylammonium bromide was added in an amount of 6g.
Comparative example 1
The catalyst was prepared according to the method of example 1. Except that the reactor is a hastelloy reaction kettle with a smooth inner wall.
Comparative example 2
A commercial conventional cyclohexene catalyst sample prepared by selective hydrogenation of benzene is used as a comparative example, the particle size of the cyclohexene catalyst sample is 3-7nm, the appearance of the cyclohexene catalyst sample is irregular particles, and an electron microscope image is shown in figure 2.
The catalysts of the present invention were all evaluated for activity by the following methods
Adding 1.96g of catalyst, zinc sulfate, zirconium dioxide and deionized water in a 1L Hastelloy autoclave, pouring into a reaction kettle, and stirring at 700 r/min; after nitrogen replacement, hydrogen replacement and pressure increase to 4MPa are carried out. Raising the temperature of the oil bath to 140 ℃ for 22 hours, increasing the rotation speed to about 1400r/min, raising the oil temperature to 145 ℃, keeping the pressure in the kettle at 5MPa, adding the raw material benzene, starting timing, and sampling and analyzing at the 6 th, 12 th, 18 th and 24 th minutes. The contents of cyclohexene, cyclohexane and benzene were analyzed by area normalization method using a gas chromatograph, and the conversion rate, selectivity and yield were calculated, and the results are shown in table 1 below. The catalysts of the present invention were evaluated in a cycle test by the following methods.
After each reaction, the upper oil phase is evaporated out, and the next reaction can be carried out. The catalyst was evaluated after 10 cycles and the catalyst was taken to measure the grain size by XRD, the results of which are shown in table 2 below.
TABLE 1
TABLE 2
| Catalyst and process for preparing same | Reaction time (min) | Conversion of benzene | Cyclohexene selectivity | Crystal grain enlargement ratio |
| Example 1 | 16 | 52.90％ | 83.70％ | 3％ |
| Example 2 | 14 | 52.20％ | 82.80％ | 4％ |
| Example 3 | 15 | 47.90％ | 83.10％ | 5％ |
| Example 4 | 14 | 53.20％ | 82.30％ | 4％ |
| Comparative example 1 | 15 | 43.80％ | 79.10％ | 13％ |
| Comparative example 2 | 16 | 44.10％ | 78.10％ | 15％ |
As can be seen from the results in tables 1 and 2 above, the catalyst prepared by the method of the present invention can achieve higher benzene conversion rate in the benzene hydrogenation process while maintaining the cyclohexene selectivity substantially unchanged, and the morphology and performance of the catalyst are substantially unchanged after the catalyst is circulated for multiple times. In comparative example 1 using a reactor having a smooth inner wall, the conversion of benzene was low, and the selectivity was also lowered at the late stage of 10 cycles, and the crystal grains were increased.
Claims (10)
1. A preparation method of a spherical twin crystal ruthenium catalyst is characterized by comprising the following steps:
1) At normal temperature, precursor of active ingredient Ru, precursor of auxiliary agent M, reducing agent, crystal directing agent and surfactant are ultrasonically dissolved in water to make Ru 3+ The ion is 0.02-0.20 mol/L, the atomic number ratio of each component in the solution is 1 Ru, and M is 0.01-0.2; adjusting the pH =8-10 with an alkali solution;
2) Transferring the fully dissolved solution in the step 1) to a polytetrafluoroethylene kettle;
3) Sealing the polytetrafluoroethylene kettle in the step 2), and reacting for 1-10 hours at 100-200 ℃ to obtain a crystallization reaction mixture;
4) Washing the crystallization reaction mixture in step 3) with deionized water to neutrality and free of Cl - Detecting to obtain the spherical twin crystal ruthenium catalyst,
wherein, the precursor of Ru in the step 1) is ruthenium chloride,
the precursor of the auxiliary M is any one of acetate, sulfate or nitrate of M and other organic or inorganic salts, the M is any one of Mo, co, fe, la, ce and Zn,
the reducing agent is at least one selected from formaldehyde, isopropanol and ethylene glycol,
the crystal guiding agent is at least one of KBr, KCl and KI,
the surfactant is at least one selected from cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and sodium polyacrylate,
the alkali solution is NaOH or KOH aqueous solution, and the mass fraction is 3-20%.
2. The production method according to claim 1,
the precursor of the auxiliary M is sulfate of M, and M is any one of Mo, co, fe and Zn.
3. The production method according to claim 1,
the reducing agent is at least one selected from formaldehyde and isopropanol.
4. The production method according to claim 1,
the crystal directing agent is KBr.
5. The production method according to claim 1,
the surfactant is at least one selected from cetyl trimethyl ammonium bromide and sodium polyacrylate.
6. The production method according to claim 1,
the mass fraction of the alkali solution is 5-15%.
7. The production method according to claim 1,
Ru 3+ the ion concentration is 0.02-0.20 mol/L; m concentration is Ru 3+ 0.01 to 0.2 times of the ion concentration; the concentration of the crystal directing agent is 1-10g/L; the concentration of the surfactant is 10-20g/L.
8. The method of claim 1, comprising the steps of:
1) 7.95g of RuCl were added at 30 ℃ 3 ·3H 2 O, 0.2g of ZnSO 4 ·7H 2 Dissolving O, 2g of KBr and 4.7g of hexadecyl trimethyl ammonium bromide in 100ml of water by ultrasonic treatment, adding 200ml of 37% formaldehyde solution, and adjusting the pH to be =9 by using 10% KOH aqueous solution;
2) Transferring the fully dissolved solution in the step 1) to a polytetrafluoroethylene kettle;
3) Sealing the polytetrafluoroethylene kettle in the step 2), and reacting in a homogeneous reactor for 8 hours at 170 ℃ to obtain a crystallized reaction mixture;
4) Washing the crystallization reaction mixture in the step 3) by deionized water until the mixture is neutral and free of Cl - Detecting to obtain the spherical twin crystal ruthenium catalyst.
9. A spherical twin ruthenium catalyst prepared using the process of any one of claims 1 to 8.
10. A method for producing cyclohexene using the spherical twin ruthenium catalyst according to claim 9, which comprises:
hydrogenating benzene in the presence of the spherical twin crystal ruthenium catalyst to produce cyclohexene.
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| CN102319562A (en) * | 2011-09-13 | 2012-01-18 | 北京旭阳化工技术研究院有限公司 | The Preparation of catalysts method of producing cyclohexene with benzene selective hydrogenation and the catalyst for preparing through this method |
| CN102600888A (en) * | 2012-01-31 | 2012-07-25 | 湘潭大学 | Benzene hydrogenation catalyst as well as preparation method and application thereof |
| CN104525192A (en) * | 2014-12-22 | 2015-04-22 | 浙江大学 | Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene |
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| CN102319562A (en) * | 2011-09-13 | 2012-01-18 | 北京旭阳化工技术研究院有限公司 | The Preparation of catalysts method of producing cyclohexene with benzene selective hydrogenation and the catalyst for preparing through this method |
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