CN106964390A - Benzene catalyst processed and its production and use - Google Patents
Benzene catalyst processed and its production and use Download PDFInfo
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- CN106964390A CN106964390A CN201710104063.5A CN201710104063A CN106964390A CN 106964390 A CN106964390 A CN 106964390A CN 201710104063 A CN201710104063 A CN 201710104063A CN 106964390 A CN106964390 A CN 106964390A
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 462
- 239000003054 catalyst Substances 0.000 title claims abstract description 182
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 91
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 91
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 45
- -1 copper halide Chemical class 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 239000011787 zinc oxide Substances 0.000 claims abstract description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 63
- 239000007864 aqueous solution Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 39
- 239000012018 catalyst precursor Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 72
- 238000006006 cyclotrimerization reaction Methods 0.000 abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 abstract 1
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 229910052763 palladium Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 46
- 238000002360 preparation method Methods 0.000 description 31
- 239000000203 mixture Substances 0.000 description 28
- 230000003197 catalytic effect Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- 239000002243 precursor Substances 0.000 description 11
- 238000004821 distillation Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 9
- 238000011031 large-scale manufacturing process Methods 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000005060 rubber Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
- C07C2/48—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion of only hydrocarbons containing a carbon-to-carbon triple bond
-
- 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
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- Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses benzene catalyst processed and its production and use, wherein, benzene catalyst processed includes：80~99.99wt% carrier；0.01~20wt% active component, the active component is loaded on the carrier；Wherein, the active component includes：The palladium nitrate of 8~30 parts by weight；The palladium bichloride of 2~5 parts by weight；And 65~90 parts by weight copper halide, the carrier be selected from least one of titanium dioxide, zinc oxide, magnesia, CNT and graphene.Cyclotrimerization generation benzene can in a mild condition occur with catalyzing acetylene for the benzene catalyst processed, and the conversion ratio of acetylene and the selectivity of benzene are higher in reaction, it is adaptable to industrial amplification production, there is good market application foreground.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a benzene preparation catalyst, a preparation method and application thereof.
Background
Benzene, toluene, xylene and other light aromatic hydrocarbons (collectively called BTX) are used as the most basic organic chemical raw materials and widely applied to the preparation of rubber, fiber, plastic, dye and other chemical products. Currently, aromatics are mainly derived from catalytic reforming and hydrocarbon cracking in petrochemical industry (about 90%), and only about 10% are derived from coal chemical industry. In recent years, on the one hand, the gradual reduction of petroleum resources and on the other hand, the increasing demand for synthetic materials and other fine chemicals has created a higher demand for aromatic hydrocarbon production, and therefore the development of new techniques for aromatic hydrocarbon production is imperative. If acyclic simple molecules such as methane, methanol, acetylene and the like can be utilized to perform aromatization reaction, the light aromatic hydrocarbon with high added value is directly converted, and the method has important strategic significance.
Acetylene has very high reactivity and its cyclotrimerization reaction is thermodynamically strongly exothermic. However, the reaction takes place at a high temperature of 400 ℃ without the presence of a catalyst, and the reaction produces only a very small amount of benzene with the formation of a large amount of by-products. The existing reaction for catalyzing acetylene to generate benzene by adopting the catalyst has the problems of harsh reaction conditions, complex reaction feed components, easy inactivation of the catalyst and the like, and the conversion rate of acetylene and the selectivity of benzene are low.
Thus, the existing means for producing benzene from acetylene still remains to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a benzene preparation catalyst, a preparation method and application thereof. The catalyst for preparing benzene can catalyze acetylene to generate cyclotrimerization reaction under mild conditions to generate benzene, and the conversion rate of acetylene and the selectivity of benzene in the reaction are high, so that the catalyst is suitable for industrial large-scale production and has good market application prospect.
In a first aspect of the present invention, a benzene production catalyst is provided. According to an embodiment of the present invention, the benzene production catalyst comprises: 80-99.99 wt% of a carrier; 0.01-20 wt% of active component, wherein the active component is loaded on the carrier; wherein the active components comprise: 8-30 parts by weight of palladium nitrate; 2-5 parts by weight of palladium chloride; and 65-90 parts by weight of copper halide, wherein the carrier is at least one selected from titanium dioxide, zinc oxide, magnesium oxide, carbon nanotubes and graphene.
Therefore, the benzene preparation catalyst provided by the embodiment of the invention can catalyze acetylene to perform cyclotrimerization reaction under mild conditions to generate benzene, and the conversion rate of acetylene and the selectivity of benzene in the reaction are high, so that the catalyst is suitable for industrial large-scale production and has a good market application prospect.
In addition, the benzene-making catalyst according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the benzene production catalyst comprises: 90-99.99 wt% of a carrier; and 0.01-10 wt% of active components, preferably, the benzene-making catalyst comprises: 99-99.99 wt% of a carrier; and 0.01 to 1 wt% of an active component. Thus, the catalytic activity of the benzene production catalyst can be remarkably improved.
In some embodiments of the invention, the active component comprises: 15-30 parts by weight of palladium nitrate; 2-4 parts by weight of palladium chloride; and 65-90 parts by weight of copper halide, preferably, the active component comprises: 15-25 parts by weight of palladium nitrate; 2.5 to 3.7 parts by weight of palladium chloride; and 75 to 90 parts by weight of a copper halide. This can further improve the catalytic activity of the benzene production catalyst.
In some embodiments of the present invention, the support is at least one selected from the group consisting of magnesium oxide, carbon nanotubes, and graphene.
In some embodiments of the invention, the support is graphene.
In some embodiments of the invention, the carrier has an average particle size of 150 to 180 microns.
In some embodiments of the invention, the copper halide is copper chloride and/or copper bromide, preferably copper chloride.
In a second aspect of the invention, a process for preparing the benzene production catalyst described in the previous examples is provided. According to an embodiment of the invention, the method comprises: mixing palladium nitrate, palladium chloride and copper halide with water respectively so as to obtain a palladium nitrate aqueous solution, a palladium chloride aqueous solution and a copper halide aqueous solution; mixing the palladium nitrate aqueous solution, the palladium chloride aqueous solution and the copper halide aqueous solution with a carrier according to a preset proportion and carrying out impregnation treatment so as to obtain a benzene-making catalyst precursor; and roasting the benzene-making catalyst precursor to obtain the benzene-making catalyst.
Thus, according to the embodiment of the present invention, the method comprises preparing the active components palladium nitrate, palladium chloride and copper halide into aqueous solutions, respectively, impregnating the carrier with the aqueous solution of palladium nitrate, the aqueous solution of palladium chloride and the aqueous solution of copper halide to load the active components on the carrier to obtain the benzene-making catalyst precursor, and then calcining the benzene-making catalyst precursor to obtain the benzene-making catalyst described in the previous embodiment. The catalyst for preparing benzene can catalyze acetylene to generate cyclotrimerization reaction under mild conditions to generate benzene, and the conversion rate of acetylene and the selectivity of benzene in the reaction are high, so that the catalyst is suitable for industrial large-scale production and has good market application prospect.
In addition, the method for preparing the benzene production catalyst according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the immersion treatment is performed for 3 to 24 hours. Thereby, the active ingredient can be effectively supported on the carrier.
In some embodiments of the invention, the firing treatment further comprises: drying the benzene-making catalyst precursor at 100-200 ℃ for 1-5 h; carrying out first roasting treatment on the dried benzene-making catalyst precursor at the temperature of 200-400 ℃ for 2-4 h; and carrying out second roasting treatment on the benzene-making catalyst precursor subjected to the first roasting treatment at 400-700 ℃ for 2-4 h so as to obtain the benzene-making catalyst.
In a third aspect of the invention, a process for producing benzene from acetylene is provided. According to an embodiment of the invention, the method comprises: mixing the benzene-making catalyst and the solvent in a container to obtain a mixed solution; and introducing acetylene into the container, and enabling the benzene-preparing catalyst to catalyze the acetylene to react under mild conditions so as to generate benzene.
Therefore, according to the embodiment of the invention, the benzene preparation catalyst described in the previous embodiment is adopted to catalyze the cyclotrimerization reaction of acetylene under mild conditions to generate benzene, and the conversion rate of acetylene and the selectivity of benzene in the reaction are high, so that the method is suitable for industrial large-scale production and has good market application prospect.
In addition, the method for preparing benzene from acetylene according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the solvent comprises at least one selected from the group consisting of ethylene glycol, toluene, and N-methyl pyrrolidone, preferably N-methyl pyrrolidone.
In some embodiments of the invention, prior to passing acetylene into the vessel, further comprises: heating the mixed solution to 160 ℃; and continuously introducing hydrogen into the container for 2-8 hours. Thus, the catalytic activity of the benzene production catalyst can be remarkably improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a process for preparing a benzene-making catalyst according to one embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a process for producing benzene from acetylene according to one embodiment of the invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
In a first aspect of the present invention, a benzene production catalyst is provided. According to embodiments of the present invention, the benzene production catalyst may include: 80-99.99 wt% of a carrier; 0.01-20 wt% of active component, wherein the active component is loaded on the carrier; wherein the active component may include: 8-30 parts by weight of palladium nitrate; 2-5 parts by weight of palladium chloride; and 65-90 parts by weight of copper halide, wherein the carrier can be at least one selected from titanium dioxide, zinc oxide, magnesium oxide, carbon nanotubes and graphene.
According to embodiments of the present invention, the inventors have found that palladium nitrate and palladium chloride may be used as the main catalyst; the copper halide may be used as a co-catalyst, whereby the reaction time for producing benzene from acetylene can be shortened, and the inventors have found in experiments that the reaction time is hardly reduced when the content of the copper halide is less than 65 parts by weight; the addition of the carrier can not only reduce the preparation cost of the catalyst, but also improve the reaction efficiency of the catalyst.
According to an embodiment of the present invention, the above benzene production catalyst may further include: 90-99.99 wt% of a carrier; and 0.01-10 wt% of active components, preferably, the benzene-making catalyst comprises: 99-99.99 wt% of a carrier; and 0.01 to 1 wt% of an active component. Thus, the catalytic activity of the benzene production catalyst can be remarkably improved.
According to an embodiment of the present invention, the active component may further include: 15-30 parts by weight of palladium nitrate; 2-4 parts by weight of palladium chloride; and 65-90 parts by weight of copper halide, so that the catalytic activity of the benzene-making catalyst can be further improved by increasing the appropriate amount of palladium nitrate.
Preferably, the active components include: 15-25 parts by weight of palladium nitrate; 2.5 to 3.7 parts by weight of palladium chloride; and 75 to 90 parts by weight of a copper halide. This can further improve the catalytic activity of the benzene production catalyst.
The kind of the copper halide is not particularly limited according to the embodiment of the present invention, and may be selected by those skilled in the art according to actual needs, and according to the embodiment of the present invention, the copper halide may be copper chloride and/or copper bromide, preferably copper chloride. This can further improve the catalytic activity of the benzene production catalyst.
According to an embodiment of the present invention, the benzene production catalyst may include a mixture of 65 to 90 parts by weight of copper chloride and copper bromide. According to the embodiments of the present invention, the inventors have found that impurities such as hydrogen sulfide in acetylene can be removed better by using a mixture of copper chloride and copper bromide, thereby further shortening the reaction time and improving the quality of the produced benzene.
According to an embodiment of the present invention, the benzene production catalyst may include 75 to 90 parts by weight of copper chloride. According to the embodiment of the invention, the inventor finds that the efficiency of removing impurities such as hydrogen sulfide in acetylene by using 75-90 parts by weight of copper chloride can be further improved, so that the reaction time is further shortened, and the quality of the prepared benzene is improved.
According to an embodiment of the present invention, the support may be at least one selected from the group consisting of magnesium oxide, carbon nanotubes, and graphene, and according to a preferred embodiment of the present invention, the support may be graphene, whereby the catalytic activity of the benzene production catalyst may be further improved.
According to the embodiment of the present invention, the particle size of the carrier is not particularly limited, and those skilled in the art can select the carrier according to the actual requirement, and according to the specific implementation of the present invention, the average particle size of the carrier may be 150 to 180 μm. The inventors found that if the carrier particle diameter is too small, the carrier particles tend to agglomerate with each other, which is disadvantageous in dispersion; the carrier particle size is too large, so that the catalyst cannot completely permeate the carrier, and the uniform distribution of the catalyst on the carrier is not facilitated.
Therefore, according to the embodiment of the invention, the benzene preparation catalyst adopting the components and the proportion can catalyze acetylene to generate cyclotrimerization reaction under mild conditions to generate benzene, and the conversion rate of acetylene and the selectivity of benzene in the reaction are higher, so that the catalyst is suitable for industrial large-scale production and has good market application prospect.
In a second aspect of the invention, a process for preparing the benzene production catalyst described in the previous examples is provided. According to an embodiment of the invention, the method comprises: mixing palladium nitrate, palladium chloride and copper halide with water respectively so as to obtain a palladium nitrate aqueous solution, a palladium chloride aqueous solution and a copper halide aqueous solution; mixing a palladium nitrate aqueous solution, a palladium chloride aqueous solution and a copper halide aqueous solution with a carrier according to a preset proportion and carrying out impregnation treatment so as to obtain a benzene-making catalyst precursor; and roasting the precursor of the benzene-making catalyst to obtain the benzene-making catalyst.
A method for preparing a benzene production catalyst according to an embodiment of the present invention will be described in detail with reference to fig. 1, the method including:
s110: preparing the impregnating solution
In this step, palladium nitrate, palladium chloride and copper chloride are mixed with water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper halide solution. Specifically, an aqueous solution of palladium nitrate, an aqueous solution of palladium chloride and an aqueous solution of copper halide at corresponding concentrations may be prepared as the impregnation liquid, respectively, according to the loading amount of the active component and the water absorption rate of the carrier used.
According to embodiments of the present invention, the benzene production catalyst may include: 80-99.99 wt% of a carrier; 0.01-20 wt% of active component, wherein the active component is loaded on the carrier; wherein the active component may include: 8-30 parts by weight of palladium nitrate; 2-5 parts by weight of palladium chloride; and 65-90 parts by weight of copper halide, wherein the carrier can be at least one selected from titanium dioxide, zinc oxide, magnesium oxide, carbon nanotubes and graphene.
According to embodiments of the present invention, the inventors have found that palladium nitrate and palladium chloride may be used as the main catalyst; the copper halide may be used as a co-catalyst, whereby the reaction time for producing benzene from acetylene can be shortened, and the inventors have found in experiments that the reaction time is hardly reduced when the content of the copper halide is less than 65 parts by weight; the addition of the carrier can not only reduce the preparation cost of the catalyst, but also improve the reaction efficiency of the catalyst.
According to an embodiment of the present invention, the above benzene production catalyst may further include: 90-99.99 wt% of a carrier; and 0.01-10 wt% of active components, preferably, the benzene-making catalyst comprises: 99-99.99 wt% of a carrier; and 0.01 to 1 wt% of an active component. Thus, the catalytic activity of the benzene production catalyst can be remarkably improved.
According to an embodiment of the present invention, the active component may further include: 15-30 parts by weight of palladium nitrate; 2-4 parts by weight of palladium chloride; and 65-90 parts by weight of copper halide, preferably, the active component comprises: 15-25 parts by weight of palladium nitrate; 2.5 to 3.7 parts by weight of palladium chloride; and 75 to 90 parts by weight of a copper halide. This can further improve the catalytic activity of the benzene production catalyst.
The kind of the copper halide is not particularly limited according to the embodiment of the present invention, and may be selected by those skilled in the art according to actual needs, and according to the embodiment of the present invention, the copper halide may be copper chloride and/or copper bromide, preferably copper bromide. This can further improve the catalytic activity of the benzene production catalyst.
According to an embodiment of the present invention, the benzene production catalyst may include a mixture of 65 to 90 parts by weight of copper chloride and copper bromide. According to the embodiments of the present invention, the inventors have found that impurities such as hydrogen sulfide in acetylene can be removed better by using a mixture of copper chloride and copper bromide, thereby further shortening the reaction time and improving the quality of the produced benzene.
According to an embodiment of the present invention, the benzene production catalyst may include 75 to 90 parts by weight of copper chloride. According to the embodiment of the invention, the inventor finds that the efficiency of removing impurities such as hydrogen sulfide in acetylene by using 75-90 parts by weight of copper chloride can be further improved, so that the reaction time is further shortened, and the quality of the prepared benzene is improved.
S120: obtaining a catalyst precursor
In the step, a palladium nitrate aqueous solution, a palladium chloride aqueous solution and a copper halide aqueous solution are mixed with a carrier according to a predetermined ratio and subjected to impregnation treatment, so as to obtain a benzene-making catalyst precursor.
According to the examples of the present invention, the amount or ratio of the above aqueous palladium nitrate solution, aqueous palladium chloride solution and aqueous copper halide solution is not particularly limited as long as the active component can be supported on the carrier to the amount described in the previous examples.
According to the embodiment of the present invention, the immersion treatment may be performed for 3 to 24 hours, whereby the active component may be effectively supported on the carrier.
According to an embodiment of the present invention, the support may be at least one selected from the group consisting of magnesium oxide, carbon nanotubes, and graphene, and according to a preferred embodiment of the present invention, the support may be graphene, whereby the catalytic activity of the benzene production catalyst may be further improved.
According to the embodiment of the present invention, the particle size of the carrier is not particularly limited, and those skilled in the art can select the carrier according to the actual requirement, and according to the specific implementation of the present invention, the average particle size of the carrier may be 150 to 180 μm. The inventors found that if the carrier particle diameter is too small, the carrier particles tend to agglomerate with each other, which is disadvantageous in dispersion; the carrier particle size is too large, so that the catalyst cannot completely permeate the carrier, and the uniform distribution of the catalyst on the carrier is not facilitated.
S130: obtaining the benzene-preparing catalyst
In the step, the precursor of the benzene-making catalyst is roasted to obtain the benzene-making catalyst.
Firstly, according to the embodiment of the invention, the benzene-making catalyst precursor is dried for 1-5 hours at 100-200 ℃ so as to fully remove the moisture in the benzene-making catalyst precursor. And then, carrying out first roasting treatment on the dried benzene-making catalyst precursor at 200-400 ℃ for 2-4 h, and then carrying out second roasting treatment on the benzene-making catalyst subjected to the first roasting treatment at 400-700 ℃ for 2-4 h so as to obtain the benzene-making catalyst. According to the embodiment of the present invention, the inventors have found that the catalyst can obtain a certain crystal form by sequentially performing the first calcination treatment and the second calcination treatment, and form crystal grains having a certain size. Meanwhile, the fractional calcination can prevent the carrier framework material from collapsing due to too long heating time, and the catalyst can be well loaded on the carrier.
Thus, according to the embodiment of the present invention, the method comprises preparing the active components palladium nitrate, palladium chloride and copper halide into aqueous solutions, respectively, impregnating the carrier with the aqueous solution of palladium nitrate, the aqueous solution of palladium chloride and the aqueous solution of copper halide to load the active components on the carrier to obtain the benzene-making catalyst precursor, and then calcining the benzene-making catalyst precursor to obtain the benzene-making catalyst described in the previous embodiment. The catalyst for preparing benzene can catalyze acetylene to generate cyclotrimerization reaction under mild conditions to generate benzene, and the conversion rate of acetylene and the selectivity of benzene in the reaction are high, so that the catalyst is suitable for industrial large-scale production and has good market application prospect.
In a third aspect of the invention, a process for producing benzene from acetylene is provided. According to an embodiment of the invention, the method comprises: mixing the benzene-making catalyst and the solvent in a container to obtain a mixed solution; and introducing acetylene into the container, and catalyzing the acetylene to react by the benzene-preparing catalyst at normal temperature and normal pressure so as to generate benzene.
A method for preparing benzene from acetylene according to an embodiment of the present invention is described in detail below with reference to fig. 2, and includes:
s210: preparing catalyst mixed liquor
In this step, the benzene-producing catalyst described in the previous example and a solvent are mixed in a vessel to obtain a mixed solution containing the benzene-producing catalyst described in the previous example.
According to embodiments of the present invention, the benzene production catalyst may include: 80-99.99 wt% of a carrier; 0.01-20 wt% of active component, wherein the active component is loaded on the carrier; wherein the active component may include: 8-30 parts by weight of palladium nitrate; 2-5 parts by weight of palladium chloride; and 65-90 parts by weight of copper halide, wherein the carrier can be at least one selected from titanium dioxide, zinc oxide, magnesium oxide, carbon nanotubes and graphene.
According to embodiments of the present invention, the inventors have found that palladium nitrate and palladium chloride may be used as the main catalyst; the copper halide may be used as a co-catalyst, whereby the reaction time for producing benzene from acetylene can be shortened, and the inventors have found in experiments that the reaction time is hardly reduced when the content of the copper halide is less than 65 parts by weight; the addition of the carrier can not only reduce the preparation cost of the catalyst, but also improve the reaction efficiency of the catalyst.
According to an embodiment of the present invention, the above benzene production catalyst may further include: 90-99.99 wt% of a carrier; and 0.01-10 wt% of active components, preferably, the benzene-making catalyst comprises: 99-99.99 wt% of a carrier; and 0.01 to 1 wt% of an active component. Thus, the catalytic activity of the benzene production catalyst can be remarkably improved.
According to an embodiment of the present invention, the active component may further include: 15-30 parts by weight of palladium nitrate; 2-4 parts by weight of palladium chloride; and 65-90 parts by weight of copper halide, preferably, the active component comprises: 15-25 parts by weight of palladium nitrate; 2.5 to 3.7 parts by weight of palladium chloride; and 75 to 90 parts by weight of a copper halide. This can further improve the catalytic activity of the benzene production catalyst.
The kind of the copper halide is not particularly limited according to the embodiment of the present invention, and may be selected by those skilled in the art according to actual needs, and according to the embodiment of the present invention, the copper halide may be copper chloride and/or copper bromide, preferably copper bromide. This can further improve the catalytic activity of the benzene production catalyst.
According to an embodiment of the present invention, the benzene production catalyst may include a mixture of 65 to 90 parts by weight of copper chloride and copper bromide. According to the embodiments of the present invention, the inventors have found that impurities such as hydrogen sulfide in acetylene can be removed better by using a mixture of copper chloride and copper bromide, thereby further shortening the reaction time and improving the quality of the produced benzene. According to an embodiment of the present invention, the benzene production catalyst may include 75 to 90 parts by weight of copper chloride. According to the embodiment of the invention, the inventor finds that the efficiency of removing impurities such as hydrogen sulfide in acetylene by using 75-90 parts by weight of copper chloride can be further improved, so that the reaction time is further shortened, and the quality of the prepared benzene is improved.
According to an embodiment of the present invention, the support may be at least one selected from the group consisting of magnesium oxide, carbon nanotubes, and graphene, and according to a preferred embodiment of the present invention, the support may be graphene, whereby the catalytic activity of the benzene production catalyst may be further improved.
According to the embodiment of the present invention, the particle size of the carrier is not particularly limited, and those skilled in the art can select the carrier according to the actual requirement, and according to the specific implementation of the present invention, the average particle size of the carrier may be 150 to 180 μm. The inventors found that if the carrier particle diameter is too small, the carrier particles tend to agglomerate with each other, which is disadvantageous in dispersion; the carrier particle size is too large, so that the catalyst cannot completely permeate the carrier, and the uniform distribution of the catalyst on the carrier is not facilitated.
According to embodiments of the present invention, the kind of the solvent is not particularly limited and may be selected by those skilled in the art according to actual needs, and according to particular embodiments of the present invention, the solvent may include at least one selected from the group consisting of ethylene glycol, toluene, and N-methylpyrrolidone, preferably N-methylpyrrolidone, and thus, the yield and selectivity of the produced benzene may be significantly improved.
S220: introducing acetylene to react
In this step, acetylene is introduced into the vessel and the benzene-producing catalyst described in the previous example is allowed to catalyze the reaction of acetylene at normal temperature and pressure to produce benzene. Specifically, according to the embodiment of the present invention, the air in the container may be replaced with acetylene three times, so as to fill the container with an acetylene atmosphere, and then the reaction may be performed under stirring, after the reaction is completed, the catalyst in the mixed solution may be filtered, and the solvent may be removed by atmospheric distillation, so as to obtain the product benzene.
The term "normal temperature and pressure" means that the reaction system is allowed to react under natural conditions without heating or cooling, or pressurizing or depressurizing the reaction system. The catalyst for preparing benzene is adopted, so that acetylene can react at normal temperature and normal pressure to generate benzene, the conversion rate of acetylene and the selectivity of benzene are high in the reaction, and the catalyst is suitable for industrial large-scale production and has good market application prospect.
According to the specific embodiment of the invention, before the acetylene is introduced into the container, the catalyst mixed liquid in the container can be heated to 160 ℃, and then the hydrogen is continuously introduced into the container for 2-8 hours, so that the benzene-making catalyst in the mixed liquid can be reduced, and the catalytic activity of the benzene-making catalyst is further improved.
Therefore, according to the embodiment of the invention, the benzene preparation catalyst described in the previous embodiment is adopted to catalyze the cyclotrimerization reaction of acetylene under mild conditions to generate benzene, the reaction is rapid, the operation is simple, the conversion rate of acetylene and the selectivity of benzene in the reaction are high, and the method is suitable for industrial scale-up production.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
1. Preparation of benzene-making catalyst
Palladium nitrate, palladium chloride and copper chloride were mixed with deionized water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper chloride solution each having a concentration of 5 g/L. Then 3.0mL of palladium nitrate aqueous solution is measured and slowly added into a porcelain cell containing 20g of graphene carrier, and a glass rod is used for stirring in the adding process. 0.5mL of an aqueous palladium chloride solution and 6.5mL of an aqueous copper chloride solution were added to the carrier in the same manner. And standing the obtained paste for 24 hours in a ventilated environment to obtain a precursor of the benzene-preparing catalyst. Putting a benzene-making catalyst precursor into a muffle furnace for roasting, wherein the temperature control procedure is as follows: the temperature is raised to 150 ℃ over 1h, and the temperature is kept for 1 h; then the temperature is raised to 300 ℃ for 1h, and the mixture is kept at the temperature for 3 h; then the temperature is increased to 500 ℃ in 1 hour, the mixture is kept at the temperature for 3 hours, and finally the temperature is reduced to 25 ℃ in 3 hours to obtain the benzene preparation catalyst.
2. The catalyst for preparing benzene is adopted to catalyze acetylene to react to generate benzene
After 30mL of N-methylpyrrolidone was put into a 100mL flask, 4g of the above benzene production catalyst was added thereto and stirred uniformly. Before reaction, the catalyst is first reduced by introducing hydrogen at 160 deg.c for 3 hr, then cooled to 140 deg.c and replaced with acetylene for three times to fill acetylene atmosphere, and the reaction is stirred at normal pressure. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed by normal pressure distillation to obtain the product benzene. The acetylene conversion was 81% and the benzene selectivity was 91% as determined by gas chromatography.
Example 2
1. Preparation of benzene-making catalyst
Palladium nitrate, palladium chloride and copper chloride were mixed with deionized water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper chloride solution each having a concentration of 5 g/L. Then 2.4mL of palladium nitrate aqueous solution is measured and slowly added into a porcelain cell containing 20g of graphene carrier, and a glass rod is used for stirring in the adding process. 0.4mL of an aqueous palladium chloride solution and 7.2mL of an aqueous copper chloride solution were added to the support in the same manner. And standing the obtained paste for 24 hours in a ventilated environment to obtain a precursor of the benzene-preparing catalyst. Putting a benzene-making catalyst precursor into a muffle furnace for roasting, wherein the temperature control procedure is as follows: the temperature is raised to 120 ℃ over 1h, and the temperature is kept for 1 h; then the temperature is raised to 350 ℃ for 1h, and the mixture is kept at the temperature for 3 h; then the temperature is increased to 500 ℃ in 1 hour, the mixture is kept at the temperature for 3 hours, and finally the temperature is reduced to 25 ℃ in 3 hours to obtain the benzene preparation catalyst.
2. The catalyst for preparing benzene is adopted to catalyze acetylene to react to generate benzene
After 30mL of N-methylpyrrolidone was put into a 100mL flask, 4g of the above benzene production catalyst was added thereto and stirred uniformly. Before reaction, the catalyst is first reduced by introducing hydrogen at 160 deg.c for 3 hr, then cooled to 140 deg.c and replaced with acetylene for three times to fill acetylene atmosphere, and the reaction is stirred at normal pressure. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed by normal pressure distillation to obtain the product benzene. The acetylene conversion was 85% and the benzene selectivity was 93% as determined by gas chromatography.
Example 3
1. Preparation of benzene-making catalyst
Palladium nitrate, palladium chloride and copper chloride were mixed with deionized water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper chloride solution each having a concentration of 5 g/L. Then 2.2mL of palladium nitrate aqueous solution was measured and slowly added to a porcelain cell containing 20g of magnesium oxide carrier, and the mixture was stirred with a glass rod during the addition. 0.4mL of an aqueous palladium chloride solution and 7.4mL of an aqueous copper chloride solution were added to the support in the same manner. And standing the obtained paste for 24 hours in a ventilated environment to obtain a precursor of the benzene-preparing catalyst. Putting a benzene-making catalyst precursor into a muffle furnace for roasting, wherein the temperature control procedure is as follows: the temperature is raised to 120 ℃ over 1h, and the temperature is kept for 1 h; then the temperature is raised to 350 ℃ for 1h, and the mixture is kept at the temperature for 3 h; then the temperature is increased to 500 ℃ in 1 hour, the mixture is kept at the temperature for 3 hours, and finally the temperature is reduced to 25 ℃ in 3 hours to obtain the benzene preparation catalyst.
2. The catalyst for preparing benzene is adopted to catalyze acetylene to react to generate benzene
After 10mL of N-methylpyrrolidone was put into a 25mL flask, 4g of the above benzene production catalyst was added thereto and stirred uniformly. Before reaction, the catalyst is first reduced by introducing hydrogen at 160 deg.c for 3 hr, then cooled to 140 deg.c and replaced with acetylene for three times to fill acetylene atmosphere, and the reaction is stirred at normal pressure. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed by normal pressure distillation to obtain the product benzene. The acetylene conversion was 77% and the benzene selectivity was 69% as determined by gas chromatography.
Example 4
1. Preparation of benzene-making catalyst
Palladium nitrate, palladium chloride and copper chloride were mixed with deionized water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper chloride solution each having a concentration of 5 g/L. Then 1.5mL of palladium nitrate aqueous solution is measured and slowly added into a porcelain cell containing 20g of graphene carrier, and a glass rod is used for stirring in the adding process. 0.4mL of an aqueous palladium chloride solution and 8.1mL of an aqueous copper chloride solution were added to the support in the same manner. And standing the obtained paste for 24 hours in a ventilated environment to obtain a precursor of the benzene-preparing catalyst. Putting a benzene-making catalyst precursor into a muffle furnace for roasting, wherein the temperature control procedure is as follows: the temperature is raised to 120 ℃ over 1h, and the temperature is kept for 1 h; then the temperature is raised to 350 ℃ for 1h, and the mixture is kept at the temperature for 3 h; then the temperature is increased to 500 ℃ in 1 hour, the mixture is kept at the temperature for 3 hours, and finally the temperature is reduced to 25 ℃ in 3 hours to obtain the benzene preparation catalyst.
2. The catalyst for preparing benzene is adopted to catalyze acetylene to react to generate benzene
After 30mL of N-methylpyrrolidone was put into a 100mL flask, 4g of the above benzene production catalyst was added thereto and stirred uniformly. Before reaction, the catalyst is first reduced by introducing hydrogen at 160 deg.c for 3 hr, then cooled to 140 deg.c and replaced with acetylene for three times to fill acetylene atmosphere, and the reaction is stirred at normal pressure. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed by normal pressure distillation to obtain the product benzene. The acetylene conversion was 85% and the benzene selectivity was 94% as determined by gas chromatography.
Example 5
1. Preparation of benzene-making catalyst
Palladium nitrate, palladium chloride and copper chloride were mixed with deionized water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper chloride solution each having a concentration of 5 g/L. Then 1.5mL of palladium nitrate aqueous solution was weighed and slowly added into a porcelain cell containing 20g of carbon nanotube carrier, and stirred with a glass rod during the addition. 0.4mL of an aqueous palladium chloride solution and 8.1mL of an aqueous copper chloride solution were added to the support in the same manner. And standing the obtained paste for 24 hours in a ventilated environment to obtain a precursor of the benzene-preparing catalyst. Putting a benzene-making catalyst precursor into a muffle furnace for roasting, wherein the temperature control procedure is as follows: the temperature is raised to 120 ℃ over 1h, and the temperature is kept for 1 h; then the temperature is raised to 350 ℃ for 1h, and the mixture is kept at the temperature for 3 h; then the temperature is increased to 500 ℃ in 1 hour, the mixture is kept at the temperature for 3 hours, and finally the temperature is reduced to 25 ℃ in 3 hours to obtain the benzene preparation catalyst.
2. The catalyst for preparing benzene is adopted to catalyze acetylene to react to generate benzene
After 30mL of N-methylpyrrolidone was put into a 100mL flask, 4g of the above benzene production catalyst was added thereto and stirred uniformly. Before reaction, the catalyst is first reduced by introducing hydrogen at 160 deg.c for 3 hr, then cooled to 140 deg.c and replaced with acetylene for three times to fill acetylene atmosphere, and the reaction is stirred at normal pressure. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed by normal pressure distillation to obtain the product benzene. The acetylene conversion was 71% and the benzene selectivity was 88% as determined by gas chromatography.
Example 6
1. Preparation of benzene-making catalyst
Palladium nitrate, palladium chloride and copper chloride were mixed with deionized water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper chloride solution each having a concentration of 5 g/L. Then 1.5mL of palladium nitrate aqueous solution was measured and slowly added to a porcelain cell containing 20g of magnesia-based carrier, and the mixture was stirred with a glass rod during the addition. 0.4mL of an aqueous palladium chloride solution and 8.1mL of an aqueous copper chloride solution were added to the support in the same manner. And standing the obtained paste for 24 hours in a ventilated environment to obtain a precursor of the benzene-preparing catalyst. Putting a benzene-making catalyst precursor into a muffle furnace for roasting, wherein the temperature control procedure is as follows: the temperature is raised to 120 ℃ over 1h, and the temperature is kept for 1 h; then the temperature is raised to 350 ℃ for 1h, and the mixture is kept at the temperature for 3 h; then the temperature is increased to 500 ℃ in 1 hour, the mixture is kept at the temperature for 3 hours, and finally the temperature is reduced to 25 ℃ in 3 hours to obtain the benzene preparation catalyst.
2. The catalyst for preparing benzene is adopted to catalyze acetylene to react to generate benzene
After 30mL of N-methylpyrrolidone was put into a 100mL flask, 4g of the above benzene production catalyst was added thereto and stirred uniformly. Before reaction, the catalyst is first reduced by introducing hydrogen at 160 deg.c for 3 hr, then cooled to 140 deg.c and replaced with acetylene for three times to fill acetylene atmosphere, and the reaction is stirred at normal pressure. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed by normal pressure distillation to obtain the product benzene. The acetylene conversion was 80% and the benzene selectivity was 65% as determined by gas chromatography.
Comparative example 1
1. Preparation of benzene-making catalyst
Palladium nitrate, palladium chloride and copper chloride were mixed with deionized water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper chloride solution each having a concentration of 5 g/L. Then 1.5mL of aqueous palladium chloride solution was measured and slowly added to a porcelain dish containing 20g of magnesia-based carrier, and the mixture was stirred with a glass rod during the addition. 8.1mL of an aqueous solution of copper chloride was added to the support in the same manner. And standing the obtained paste for 24 hours in a ventilated environment to obtain a precursor of the benzene-preparing catalyst. Putting a benzene-making catalyst precursor into a muffle furnace for roasting, wherein the temperature control procedure is as follows: the temperature is raised to 120 ℃ over 1h, and the temperature is kept for 1 h; then the temperature is raised to 350 ℃ for 1h, and the mixture is kept at the temperature for 3 h; then the temperature is increased to 500 ℃ in 1 hour, the mixture is kept at the temperature for 3 hours, and finally the temperature is reduced to 25 ℃ in 3 hours to obtain the benzene preparation catalyst.
2. The catalyst for preparing benzene is adopted to catalyze acetylene to react to generate benzene
After 30mL of N-methylpyrrolidone was put into a 100mL flask, 4g of the above benzene production catalyst was added thereto and stirred uniformly. Before reaction, the catalyst is first reduced by introducing hydrogen at 160 deg.c for 3 hr, then cooled to 140 deg.c and replaced with acetylene for three times to fill acetylene atmosphere, and the reaction is stirred at normal pressure. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed by normal pressure distillation to obtain the product benzene. The acetylene conversion was 42% and the benzene selectivity was 60% as determined by gas chromatography.
It can be seen that if only palladium chloride is present in the catalyst, and no palladium nitrate is present, both acetylene conversion and selectivity are greatly reduced. Has a larger difference with the palladium nitrate provided by the invention.
Comparative example 2
1. Preparation of benzene-making catalyst
Palladium nitrate, palladium chloride and copper chloride were mixed with deionized water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper chloride solution each having a concentration of 5 g/L. Then 1.5mL of palladium nitrate aqueous solution was measured and slowly added to a porcelain cell containing 20g of alumina support, and during the addition, stirring was performed with a glass rod. 0.4mL of an aqueous palladium chloride solution and 8.1mL of an aqueous copper chloride solution were added to the support in the same manner. And standing the obtained paste for 24 hours in a ventilated environment to obtain a precursor of the benzene-preparing catalyst. Putting a benzene-making catalyst precursor into a muffle furnace for roasting, wherein the temperature control procedure is as follows: the temperature is raised to 120 ℃ over 1h, and the temperature is kept for 1 h; then the temperature is raised to 350 ℃ for 1h, and the mixture is kept at the temperature for 3 h; then the temperature is increased to 500 ℃ in 1 hour, the mixture is kept at the temperature for 3 hours, and finally the temperature is reduced to 25 ℃ in 3 hours to obtain the benzene preparation catalyst.
2. The catalyst for preparing benzene is adopted to catalyze acetylene to react to generate benzene
After 30mL of N-methylpyrrolidone was put into a 100mL flask, 4g of the above benzene production catalyst was added thereto and stirred uniformly. Before reaction, the catalyst is first reduced by introducing hydrogen at 160 deg.c for 3 hr, then cooled to 140 deg.c and replaced with acetylene for three times to fill acetylene atmosphere, and the reaction is stirred at normal pressure. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed by normal pressure distillation to obtain the product benzene. The acetylene conversion was 55% and the benzene selectivity was 80% as determined by gas chromatography.
It can be seen that when the alumina carrier is used to support the catalyst, although the selectivity of benzene is kept high, the conversion rate of acetylene is greatly reduced, which is a certain difference from the carrier proposed by the present invention.
Comparative example 3
1. Preparation of benzene-making catalyst
Palladium nitrate, palladium chloride and copper chloride were mixed with deionized water, respectively, to obtain an aqueous palladium nitrate solution, an aqueous palladium chloride solution and an aqueous copper chloride solution each having a concentration of 5 g/L. Then 1.5mL of palladium nitrate aqueous solution was weighed and slowly added into a porcelain cell containing 20g of molecular sieve carrier, and the mixture was stirred with a glass rod during the addition. 0.4mL of an aqueous palladium chloride solution and 8.1mL of an aqueous copper chloride solution were added to the support in the same manner. And standing the obtained paste for 24 hours in a ventilated environment to obtain a precursor of the benzene-preparing catalyst. Putting a benzene-making catalyst precursor into a muffle furnace for roasting, wherein the temperature control procedure is as follows: the temperature is raised to 120 ℃ over 1h, and the temperature is kept for 1 h; then the temperature is raised to 350 ℃ for 1h, and the mixture is kept at the temperature for 3 h; then the temperature is increased to 500 ℃ in 1 hour, the mixture is kept at the temperature for 3 hours, and finally the temperature is reduced to 25 ℃ in 3 hours to obtain the benzene preparation catalyst.
2. The catalyst for preparing benzene is adopted to catalyze acetylene to react to generate benzene
After 30mL of N-methylpyrrolidone was put into a 100mL flask, 4g of the above benzene production catalyst was added thereto and stirred uniformly. Before reaction, the catalyst is first reduced by introducing hydrogen at 160 deg.c for 3 hr, then cooled to 140 deg.c and replaced with acetylene for three times to fill acetylene atmosphere, and the reaction is stirred at normal pressure. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed by normal pressure distillation to obtain the product benzene. The acetylene conversion was 50% and the benzene selectivity was 77% as determined by gas chromatography.
It can be seen that when a molecular sieve support is used as the catalyst, although the selectivity of benzene is high, the conversion rate of acetylene is rapidly reduced, and the effect is lower than that of the catalyst support provided by the invention.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A benzene-making catalyst, comprising: 80-99.99 wt% of a carrier; 0.01-20 wt% of active component, wherein the active component is loaded on the carrier;
wherein,
the active components comprise: 8-30 parts by weight of palladium nitrate; 2-5 parts by weight of palladium chloride; and 65-90 parts by weight of copper halide, wherein the carrier is at least one selected from titanium dioxide, zinc oxide, magnesium oxide, carbon nanotubes and graphene.
2. The benzene-making catalyst according to claim 1, comprising: 90-99.99 wt% of a carrier; and 0.01 to 10 wt% of an active component.
3. The benzene-making catalyst according to claim 1, wherein the active component comprises: 15-30 parts by weight of palladium nitrate; 2-4 parts by weight of palladium chloride; and 65 to 90 parts by weight of a copper halide.
4. The benzene production catalyst according to any one of claims 1 to 3, wherein the carrier is at least one selected from the group consisting of magnesium oxide, carbon nanotubes, and graphene.
5. A method of preparing the benzene-making catalyst of any one of claims 1-4, comprising:
mixing palladium nitrate, palladium chloride and copper halide with water respectively so as to obtain a palladium nitrate aqueous solution, a palladium chloride aqueous solution and a copper halide aqueous solution;
mixing the palladium nitrate aqueous solution, the palladium chloride aqueous solution and the copper halide aqueous solution with a carrier according to a preset proportion and carrying out impregnation treatment so as to obtain a benzene-making catalyst precursor; and
and roasting the benzene-making catalyst precursor to obtain the benzene-making catalyst.
6. The method according to claim 5, wherein the immersion treatment is carried out for a time of 3 to 24 hours.
7. The method of claim 5, wherein the firing process further comprises:
drying the benzene-making catalyst precursor at 100-200 ℃ for 1-5 h;
carrying out first roasting treatment on the dried benzene-making catalyst precursor at the temperature of 200-400 ℃ for 2-4 h; and
and carrying out second roasting treatment on the benzene-making catalyst precursor subjected to the first roasting treatment at 400-700 ℃ for 2-4 h so as to obtain the benzene-making catalyst.
8. A process for producing benzene from acetylene, comprising:
mixing the benzene production catalyst according to any one of claims 1 to 4 with a solvent in a container to obtain a mixed solution;
and introducing acetylene into the container, and catalyzing the acetylene to react by the benzene-preparing catalyst at normal temperature and normal pressure so as to generate benzene.
9. The method according to claim 8, wherein the solvent comprises at least one selected from the group consisting of ethylene glycol, toluene, and N-methylpyrrolidone.
10. The method of claim 8, further comprising, prior to passing acetylene into the vessel:
heating the mixed solution to 160 ℃;
and continuously introducing hydrogen into the container for 2-8 hours.
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| CN109207997A (en) * | 2018-03-21 | 2019-01-15 | 中国航空制造技术研究院 | The method that laser-impact prepares nano-carbon material |
| CN113559924A (en) * | 2021-07-28 | 2021-10-29 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN115055201A (en) * | 2022-05-18 | 2022-09-16 | 汕尾职业技术学院 | Catalyst for preparing benzene through acetylene aromatization reaction and preparation and application thereof |
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| CN109207997A (en) * | 2018-03-21 | 2019-01-15 | 中国航空制造技术研究院 | The method that laser-impact prepares nano-carbon material |
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| CN113559924A (en) * | 2021-07-28 | 2021-10-29 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN113559924B (en) * | 2021-07-28 | 2023-10-03 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN115055201A (en) * | 2022-05-18 | 2022-09-16 | 汕尾职业技术学院 | Catalyst for preparing benzene through acetylene aromatization reaction and preparation and application thereof |
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