CN110773203A - Catalyst for preparing cyclohexene by selective hydrogenation of benzene and preparation method and use method thereof - Google Patents
Catalyst for preparing cyclohexene by selective hydrogenation of benzene and preparation method and use method thereof Download PDFInfo
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- CN110773203A CN110773203A CN201911077180.2A CN201911077180A CN110773203A CN 110773203 A CN110773203 A CN 110773203A CN 201911077180 A CN201911077180 A CN 201911077180A CN 110773203 A CN110773203 A CN 110773203A
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 126
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 61
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 61
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 57
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 21
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical group [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- -1 zinc sulfate compound salt Chemical class 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QORYBJZFIBBDSH-UHFFFAOYSA-N ruthenium zinc Chemical compound [Zn].[Zn].[Zn].[Ru] QORYBJZFIBBDSH-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004846 x-ray emission 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 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
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
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- 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
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- 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
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Abstract
The invention provides a catalyst for preparing cyclohexene by benzene selective hydrogenation, a preparation method and a use method thereof, wherein the catalyst is composed of nano Ru, hexagonal zinc sulfate composite salt, zinc sulfate and water, wherein the weight ratio of the nano Ru: hexagonal zinc sulfate complex salt: zinc sulfate: the mass ratio of water is 1: (0.1-10): (1-50): (10-300). The catalyst of the invention has simple preparation, can improve the conversion rate of benzene and the selectivity and yield of cyclohexene, and is obviously higher than the catalytic performance of the current industrial catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for preparing cyclohexene through selective hydrogenation of benzene, and a preparation method and a use method thereof.
Background
Cyclohexene is an important organic chemical intermediate and is widely used for the production of nylon 6, nylon 66, polyamide, polyester and other fine chemicals. Conventional industrial methods for preparing cyclohexene include cyclohexanol dehydration, halogenated cyclohexane dehydrohalogenation, and the like. The traditional method uses cyclohexanol and other raw materials with higher cost, and has complex process and more byproducts, so that the cyclohexene production cost is higher. The selective hydrogenation of benzene to prepare cyclohexene has the advantages of simple reaction route, high utilization rate of carbon atoms and the like, and simultaneously, the benzene with low cost is selected as the raw material, so that the production economy is improved. However, thermodynamically complete hydrogenation of benzene to cyclohexane is favored over selective hydrogenation of benzene to cyclohexene. Therefore, the development of a catalyst with high conversion and high cyclohexene selectivity is the key of the technology.
The activity of the catalyst for preparing cyclohexene by benzene selective hydrogenation and the cyclohexene selectivity are always the key problems in production. At present, the common benzene conversion rate of the industrial ruthenium-zinc catalyst is 40%, the cyclohexene selectivity is about 80%, the yield of the cyclohexene is relatively low, and meanwhile, the subsequent separation process generates high energy consumption. Meanwhile, the preparation of the ruthenium-zinc catalyst usually adopts a coprecipitation method, and precipitates are dispersed and have particle sizes in the preparation process, so that the performance of the catalyst is directly influenced. The development of a new catalyst to improve the conversion rate of benzene and the selectivity of cyclohexene is a problem to be solved urgently.
Disclosure of Invention
In view of the above, the invention aims to provide a catalyst for preparing cyclohexene through selective hydrogenation of benzene, a preparation method and a use method thereof.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a catalyst for preparing cyclohexene by selective hydrogenation of benzene comprises nanometer Ru, hexagonal zinc sulfate composite salt, zinc sulfate and water, wherein the weight ratio of the nanometer Ru: hexagonal zinc sulfate complex salt: zinc sulfate: the mass ratio of water is 1: (0.1-10): (1-50): (10-300); preferably, 1: (0.1-5): (10-20): (120-150); preferably, 1: (1.4-1.7): (11-18): 130.
preferably, the grain size of the nano Ru is 2-8 nm; the crystal grain size of the hexagonal zinc sulfate composite salt is 20-50 mu m, and the molecular formula is ZnSO
4·3Zn(OH)
2·3H
2O and ZnSO
4·3Zn(OH)
2·5H
2A mixture of O. The grain size refers to the size of the grains and is data obtained by high power transmission electron microscopy (HRTEM).
The invention also provides a method for preparing the catalyst for preparing cyclohexene by benzene selective hydrogenation, which comprises the following steps,
1) dissolving zinc sulfate and hexadecyl trimethyl ammonium bromide in water, adjusting the pH value of the mixed solution to 8-11, transferring the solution into a hydrothermal reaction kettle, and heating to the temperature of 120-160 ℃ for reaction for 12-20 hours; filtering or centrifuging and washing the obtained solution, and drying at 60 ℃ to obtain hexagonal zinc sulfate composite salt powder; preferably, the pH value is adjusted to 10, the mixture is heated to 140 ℃ in a hydrothermal reaction kettle for 16 hours of reaction, and the mixture is dried at 60 ℃;
2) mixing nano Ru, zinc sulfate composite salt and zinc sulfate in an aqueous solution, and reacting for 1-3 hours at 70-100 ℃ to obtain the catalyst for preparing cyclohexene through selective hydrogenation of benzene.
The purpose of mixing nanometer Ru, zinc sulfate composite salt, zinc sulfate in aquatic is that the better attaching to of zinc sulfate composite salt is on Ru under having the zinc sulfate effect, increases the interact of Ru and zinc sulfate composite salt. If benzene is added directly for hydrogenation without mixing, the selectivity of the catalyst is affected and is lower than that of the mixed hydrogenation.
Preferably, the preparation method of the nano Ru comprises the steps of reducing a suspension formed by soluble Ru salt and an alkali solution in a high-pressure reaction kettle in the atmosphere of hydrogen to obtain the nano Ru; the alkali is one of sodium carbonate, ammonia water and sodium hydroxide, and the soluble Ru salt is ruthenium acetate or ruthenium trichloride.
Preferably, the preparation of the nano Ru comprises the following steps:
(1) preparing a mixed solution of 1-5mol/L soluble Ru salt solution and 3-8mol/L alkali solution, heating to 50-120 ℃, continuously stirring, and reacting for 2-10 hours;
(2) and transferring the solution into a high-pressure reaction kettle, reducing for 2-8 hours at the temperature of 100-200 ℃ and under the hydrogen pressure of 1-10MPa, cooling to obtain a black solid, washing, and drying in vacuum to obtain the nano Ru.
The catalyst or the catalyst prepared by the preparation method is applied to the preparation of the cyclohexene catalyst by selective hydrogenation of benzene.
The invention also provides a method for preparing a cyclohexene catalyst by benzene selective hydrogenation, which is characterized by comprising the following steps: a catalyst prepared using the catalyst as described above or the preparation method as described above; the method comprises the following steps:
1) adding catalyst and ZrO into high-pressure kettle
2And water, after sealing, replacing 2-4 times with nitrogen, replacing 4-7 times with hydrogen, maintaining the hydrogen pressure at 5MPa, and maintaining the stirring speed at 500-800 r/min;
2) heating to 150 deg.c, adding benzene and reacting for 5-50 min.
Preferably, the mass ratio of the catalyst, ZrO2 and water is 1: (3-8): (120-180); the mass ratio of the catalyst to benzene is 1: (80-100).
Compared with the prior art, the catalyst and the preparation method thereof have the following advantages:
1, the preparation steps of the catalyst are simple, the characteristics of complex preparation process and difficult repetition of a coprecipitation method or an impregnation method are avoided, and the catalyst is easy for industrial production;
2. the hexagonal zinc sulfate composite salt prepared by the invention has large specific surface area, and simultaneously utilizes the unique hexagonal flaky structure, thereby being beneficial to enhancing the internal diffusion of hydrogen and the timely separation of cyclohexene in the reaction process and promoting the improvement of reaction activity and selectivity;
3. the ruthenium-zinc catalyst used in industry usually has a benzene conversion rate of 40% and a cyclohexene selectivity of about 80%, while the catalyst prepared by the invention has a benzene conversion rate of 60% and a selectivity of 87%, which is much higher than the performance of industrial catalysts.
4. The catalyst disclosed by the invention has higher conversion rate and selectivity, so that the energy consumption in the subsequent separation process is reduced, and the economic benefit of the whole process is effectively improved.
Drawings
Fig. 1 is a scanning electron microscope image of hexagonal zinc sulfate complex salt prepared in the example of the present invention.
Fig. 2 is an XRD spectrum of zinc sulfate complex salt prepared in the example of the present invention;
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
In the following examples, the catalyst evaluation was carried out by the following methods:
the hydrogenation performance of the catalyst was examined in a 1L mechanically stirred reaction autoclave. Adding a certain amount of the mixture into an autoclaveCatalyst of specific ratio, ZrO
2And water. After sealing, replacing 3 times with nitrogen, replacing 5 times with hydrogen, maintaining the hydrogen pressure at 5MPa, maintaining the stirring speed at 800r/min, heating to 150 ℃, adding benzene, simultaneously increasing the stirring speed to 1300r/min, and starting timing. Sampling at fixed time in the reaction process, and analyzing the content of cyclohexene, cyclohexane and benzene by using a gas chromatograph. Wherein the catalyst is ZrO
2And water in a mass ratio of 1: 5: 150; the mass ratio of the catalyst to benzene is 1: 90.
example 1
Synthesis of Nano Ru
Preparing a mixed solution of 1mol/L ruthenium trichloride solution and 3mol/L sodium hydroxide solution, heating to 70 ℃, continuously stirring, and reacting for 2 hours. And transferring the solution into a high-pressure reaction kettle, reducing for 5 hours at 130 ℃ and under the hydrogen pressure of 4MPa, cooling to obtain a black solid, washing, and drying in vacuum to obtain the nano Ru.
Synthetic hexagonal zinc sulfate composite salt
60g of zinc sulfate and 4g of hexadecyl trimethyl ammonium bromide are dissolved in 500mL of water, the pH value of the mixed solution is adjusted to 10, the solution is transferred to a hydrothermal reaction kettle, and the solution is heated to 140 ℃ for reaction for 16 hours. Filtering or centrifuging and washing the obtained solution, and drying at 60 ℃ to obtain the hexagonal zinc sulfate composite salt powder.
Selective hydrogenation catalyst for synthesizing benzene
Mixing nanometer Ru, zinc sulfate composite salt and zinc sulfate in water solution, wherein the ratio of nanometer Ru: zinc sulfate compound salt: zinc sulfate: the weight of water is respectively 2g, 0.6g, 30g and 260g, and the catalyst for preparing cyclohexene by benzene selective hydrogenation is obtained after reaction for 2 hours at 80 ℃. The catalyst was evaluated, and the evaluation results are shown in table 1.
The catalyst synthesized in example 1 was subjected to XRF analysis (X-ray fluorescence spectroscopy) and the results were as follows:
| test element | Element content |
| Ru | 6.13％ |
| ZnO | 45.30％ |
| SO 3 | 48.57％ |
Example 2
Mixing nanometer Ru, zinc sulfate composite salt and zinc sulfate in water solution, wherein the ratio of nanometer Ru: zinc sulfate compound salt: zinc sulfate: the water masses were 2g, 1.5g, 30g and 260g, respectively, and the evaluation results are shown in Table 1 under the same conditions as in example 1.
Example 3
Mixing nanometer Ru, zinc sulfate composite salt and zinc sulfate in water solution, wherein the ratio of nanometer Ru: zinc sulfate compound salt: zinc sulfate: the water masses were 2g, 3g, 30g and 260g, respectively, and the evaluation results are shown in Table 1 under the same conditions as in example 1.
Comparative example 1
Mixing nano Ru and zinc sulfate in a water solution, wherein the ratio of nano Ru: zinc sulfate: the water masses were 2g, 30g and 260g, respectively, i.e., no hexagonal zinc sulfate complex salt was added as a reference experiment, the other conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Comparative example 2
Synthesis of Nano Ru
Preparing a mixed solution of 1mol/L ruthenium trichloride solution and 3mol/L sodium hydroxide solution, heating to 70 ℃, continuously stirring, and reacting for 2 hours. And transferring the solution into a high-pressure reaction kettle, reducing for 5 hours at 130 ℃ and under the hydrogen pressure of 4MPa, cooling to obtain a black solid, washing, and drying in vacuum to obtain the nano Ru.
Synthesis of irregular shape zinc sulfate composite salt
8.4g of NaOH were dissolved in 1.5L of water, and 40g of zinc sulfate were dissolved in 1L of water, and mixed with each other under magnetic stirring for 1 hour. Centrifuging the obtained suspension, and vacuum drying at 80 deg.C to obtain irregular zinc sulfate composite salt.
Selective hydrogenation catalyst for synthesizing benzene
Mixing nanometer Ru, zinc sulfate composite salt and zinc sulfate in water solution, wherein the ratio of nanometer Ru: zinc sulfate compound salt: zinc sulfate: the weight of water is respectively 2g, 3g, 30g and 260g, and the catalyst for preparing cyclohexene by benzene selective hydrogenation is obtained after reaction for 2 hours at 80 ℃. The catalyst was evaluated, and the evaluation results are shown in table 1.
TABLE 1 evaluation results of catalysts in examples and comparative examples
As can be seen from the results in Table 1, in comparative example 1, only nano Ru is used as the catalyst, no zinc sulfate complex salt is added, no cyclohexene is generated, and all benzene is converted into cyclohexane. In example 3 and comparative example 2, the catalysts containing the irregularly shaped zinc sulfate complex salt had lower conversion and selectivity than the catalysts containing the hexagonal zinc sulfate complex salt, which were determined by the unique structure and specific surface area of the hexagonal zinc sulfate complex salt. In examples 1 to 3, the conversion rate of benzene decreases and the selectivity of cyclohexene increases with the increase of the hexagonal zinc sulfate complex salt, and when the addition amount of the hexagonal zinc sulfate complex salt is 3g, the conversion rate of benzene, the selectivity and the yield of cyclohexene are 67.3%, 88.2% and 59.4% respectively, which are higher than the performances of the existing industrial catalysts, and thus, the catalyst can meet the needs of industrial production and has good industrial prospects.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The catalyst for preparing cyclohexene by selective hydrogenation of benzene is characterized by consisting of nano Ru, hexagonal zinc sulfate composite salt, zinc sulfate and water, wherein the ratio of nano Ru: hexagonal zinc sulfate complex salt: zinc sulfate: the mass ratio of water is 1: (0.1-10): (1-50): (10-300); preferably, 1: (0.1-5): (10-20): (120-150); preferably, 1: (1.4-1.7): (11-18): 130.
2. the catalyst for preparing cyclohexene through benzene selective hydrogenation according to claim 1, which is characterized in that: the average grain diameter of the nanometer Ru is 2-8 nm; the average grain diameter of the crystal grains of the hexagonal zinc sulfate composite salt is 20-50 mu m, and the molecular formula is ZnSO
4·3Zn(OH)
2·3H
2O and ZnSO
4·3Zn(OH)
2·5H
2A mixture of O.
3. A process for preparing a catalyst for selective hydrogenation of benzene to cyclohexene as claimed in claim 1 or 2, wherein: comprises the following steps of (a) carrying out,
1) dissolving zinc sulfate and hexadecyl trimethyl ammonium bromide in water, adjusting the pH value of the mixed solution to 8-11, transferring the solution into a hydrothermal reaction kettle, and heating to the temperature of 120-160 ℃ for reaction for 12-20 hours; filtering or centrifuging and washing the obtained solution, and drying at 60 ℃ to obtain hexagonal zinc sulfate composite salt powder; preferably, the pH value is adjusted to 10, the mixture is heated to 140 ℃ in a hydrothermal reaction kettle for 16 hours of reaction, and the mixture is dried at 60 ℃;
2) mixing nano Ru, zinc sulfate composite salt and zinc sulfate in an aqueous solution, and reacting for 1-3 hours at 70-100 ℃ to obtain the catalyst for preparing cyclohexene through selective hydrogenation of benzene.
4. The production method according to claim 3, characterized in that: the preparation method of the nano Ru comprises the steps of reducing a suspension formed by soluble Ru salt and an alkali solution in a high-pressure reaction kettle in the atmosphere of hydrogen to obtain the nano Ru; the alkali is one of sodium carbonate, ammonia water and sodium hydroxide, and the soluble Ru salt is ruthenium acetate or ruthenium trichloride.
5. The production method according to claim 3 or 4, characterized in that: the preparation of the nano Ru comprises the following steps:
(1) preparing a mixed solution of 1-5mol/L soluble Ru salt solution and 3-8mol/L alkali solution, heating to 50-120 ℃, continuously stirring, and reacting for 2-10 hours;
(2) and transferring the solution into a high-pressure reaction kettle, reducing for 2-8 hours at the temperature of 100-200 ℃ and under the hydrogen pressure of 1-10MPa, cooling to obtain a black solid, washing, and drying in vacuum to obtain the nano Ru.
6. Use of the catalyst according to claim 1 or 2 or the catalyst prepared by the preparation method according to any one of claims 3 to 5 in a catalyst for preparing cyclohexene by selective hydrogenation of benzene.
7. A method for preparing a cyclohexene catalyst by benzene selective hydrogenation is characterized by comprising the following steps: a catalyst produced using the catalyst according to claim 1 or 2 or the production method according to any one of claims 3 to 5; the method comprises the following steps:
1) adding a catalyst, ZrO2 and water into the autoclave, sealing, replacing for 2-4 times with nitrogen, replacing for 4-7 times with hydrogen, maintaining the hydrogen pressure at 5MPa, and maintaining the stirring speed at 500-800 r/min;
2) heating to 150 deg.c, adding benzene and reacting for 5-50 min.
8. The method for preparing cyclohexene catalyst by benzene selective hydrogenation as claimed in claim 7, wherein: the mass ratio of the catalyst, ZrO2 and water is 1: (3-8): (120-180); the mass ratio of the catalyst to benzene is 1: (80-100).
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