CN112824361B - Method for preparing p-xylene by efficiently catalyzing 4-methyl-3-cyclohexene formaldehyde conversion by nickel-iron bimetallic catalyst - Google Patents
Method for preparing p-xylene by efficiently catalyzing 4-methyl-3-cyclohexene formaldehyde conversion by nickel-iron bimetallic catalyst Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2076—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)- moiety is eliminated
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a method for preparing paraxylene by efficiently catalyzing 4-methyl-3-cyclohexene formaldehyde to be converted by a nickel-iron bimetallic catalyst. The catalyst is an alumina-loaded bimetallic catalyst, 4-methyl-3-cyclohexene formaldehyde is subjected to dehydrogenation aromatization and hydrodeoxygenation reactions at the temperature of 100-plus-300 ℃ under the action of a nickel-iron bimetallic catalyst to efficiently generate p-xylene, the nickel-iron bimetallic catalyst can be prepared by an impregnation method, and the 4-methyl-3-cyclohexene formaldehyde catalytic reaction is carried out in a fixed bed reactor. N-hexane is used as a solvent, and the 4-methyl-3-cyclohexene formaldehyde solution is pumped into a reaction tube by a high-pressure flow pump or passes through a catalyst bed under the sweeping of carrier gas to obtain the p-xylene. The reaction process has simple process, high yield, high p-xylene yield up to over 93%, simple catalyst preparation, high activity, low cost and easy obtaining.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a method for preparing paraxylene by using 4-methyl-3-cyclohexene formaldehyde as a raw material under the action of a nickel-iron bimetallic catalyst.
Background
Aromatic chemicals are important basic chemical raw materials. Triphenyl (p-xylene (PX), toluene and benzene) and oxygen-containing aromatic chemicals are first-level basic chemical raw materials for producing three synthetic materials (synthetic resin, synthetic fiber and synthetic rubber) and high-added-value organic chemicals, and play an irreplaceable role in meeting the daily life needs of people and the development of national economy. In particular, PX, which is a key product starting from the chain of the aromatic hydrocarbon industry, is a basic monomer for producing polyethylene terephthalate (PET). With the rapid development of the global polyester industry, the demand for PX is increasing year by year. A typical PX production process is catalytic reforming of naphtha to obtain the carbon octa-aromatics, which are then separated from the boiling point near isomer mixture by multi-stage separation or molecular sieve simulated moving bed adsorptive separation techniques. Since China is richer in coal than petroleum, experts have developed routes for producing methanol and methanol aromatics from coal and separating p-xylene from aromatics (petrochemical technology and economy, 2013,29-3-14)
However, fossil resources are non-renewable energy, energy demand is increasing with economic development, fossil energy is gradually exhausted, and the use of fossil energy also causes problems of greenhouse effect, environmental pollution and the like. Therefore, the development and utilization of clean renewable resources, and the production of chemical products and fuels by taking renewable biomass resources as raw materials are one of the feasible methods for solving the problems of energy exhaustion and environmental pollution. In addition, in the process of joint production of aromatic hydrocarbon, xylene is obtained through the steps of hydrogenation, reforming, aromatic hydrocarbon conversion, separation and the like under the conditions of a catalyst and high temperature and pressure, the process route is long, the energy consumption is high, and the development of a short and efficient conversion technology has important significance for industrial production.
Based on the above background, in recent years, various energy petrochemical companies, research institutions and colleges all have a strong interest in biomass-to-aromatics technology, and a plurality of routes for preparing PX are developed. Biomass gasification is one of the important directions for biomass utilization, and synthesis gas obtained by biomass gasification can be used as a source of carbonization chemical engineering for producing various chemical products such as methanol, aromatic hydrocarbon, synthetic oil and the like. At present, there are two main process routes for preparing aromatic hydrocarbon by using synthesis gas: the synthetic gas is subjected to Fischer-Tropsch synthesis of aromatic hydrocarbon, and the synthetic gas is subjected to methanol preparation of aromatic hydrocarbon. Professor Martin Beijing university adopts Na-Zn-Fe5C2Mechanical mixing with HZSM-5 with porous grade, a breakthrough in aromatics production from synthesis gas was made (Chemistry,2017,3(2): 323-. A research team brought by the research staff of the application Chemical system Ailanthi Fangli and Yanglini researchers (Shanxi coal Chemical institute of Chinese academy of sciences) of the Japan national Fushan university successfully designs and develops a novel catalyst, and the direct efficient directional conversion of synthesis gas is realized on the catalyst to prepare PX (Chemical Science, 2017,8, 7941-one 7946.). In 2009, Gevo and Xulongya researchers of Dalian nationality developed a route for synthesizing PX from butanol produced from renewable biomass resources as raw material, isobutylene was produced by dehydration reaction of isobutanol, and dimerization of the obtained isobutyleneC8 olefin is obtained, and C8 olefin is subjected to cyclization reaction to obtain a renewable PX product (Petro Chemical News, 2011-11-28.). The preparation of p-dimethylbenzene (ACS Catalysis,2012,2(6),398-402, Green Chemistry,2012,14(11):3114) by using bio-based 2, 5-Dimethylfuran (DMF) and ethylene as raw materials is more selective than the route researched by the previous people, but the cost for obtaining DMF from biomass is too high at present, and the large-scale preparation is difficult to realize.
Disclosure of Invention
The invention provides a nickel-iron bimetallic catalyst, which enables 4-methyl-3-cyclohexene formaldehyde to simultaneously carry out an arylation reaction and a hydrodeoxygenation reaction in a fixed bed reactor to prepare p-xylene, and the reaction process is accompanied by the generation of a byproduct toluene.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a method for preparing paraxylene by efficiently catalyzing 4-methyl-3-cyclohexene formaldehyde to convert by a nickel-iron bimetallic catalyst, wherein 4-methyl-3-cyclohexene formaldehyde solution is blown from a raw material bottle by carrier gas or directly injected into a gas-solid phase reactor filled with the nickel-iron bimetallic catalyst by a high-pressure flow pump, and catalytic dehydrogenation of a six-membered ring and hydrodeoxygenation reaction of aldehyde groups simultaneously occur in the temperature range of 100-300 ℃ to generate the paraxylene.
Based on the technical scheme, the preferable solvent for dissolving the 4-methyl-3-cyclohexene formaldehyde solution is N-hexane, 1, 4-dioxane and N-alkyl pyrrolidone, and the N-hexane is preferable.
Based on the technical scheme, the concentration of the 4-methyl-3-cyclohexene formaldehyde in the solvent is preferably 50-500 mg/mL.
Based on the technical scheme, preferably, the carrier gas is nitrogen, hydrogen, helium, preferably hydrogen.
Based on the technical scheme, preferably, the catalyst is a supported nickel-iron bimetallic catalyst and comprises an active component and a carrier; the active component is a nickel-iron bimetal; the carrier is Al2O3The specific surface area of the carrier is more than 200m2G, pore volume > 0.75m3(ii)/g; the iron componentThe content of nickel component on the catalyst is 1wt% to 15wt%, and the content of nickel component on the catalyst is 1 wt%.
Based on the technical scheme, preferably, after the 4-methyl-3-cyclohexene formaldehyde reaction raw material solution is heated to 150 ℃, the raw material steam is transferred to the gas-solid phase reactor by the carrier gas for reaction.
Based on the technical scheme, preferably, the 4-methyl-3-cyclohexene formaldehyde solution reaction raw material is injected into a gas-solid phase reactor for reaction through a high-pressure constant flow pump.
Based on the above technical scheme, preferably, the reaction is carried out in a gas-solid phase reactor; the reaction pressure is not particularly limited, and the pressure generated by the closed system is preferably 0.1MPa-0.2 MPa; the temperature of the reaction is 150-250 ℃.
Based on the technical scheme, preferably, the reaction product is led out from the gas-solid phase reactor and then is collected by a cooler, and the temperature of the cooler is controlled below-10 ℃ by a frozen salt bath so as to ensure that the product is sufficiently cooled and collected.
In particular to a method for producing paraxylene by dehydrogenation reaction and hydrodeoxygenation reaction of 4-methyl-3-cyclohexene formaldehyde and 100-300 ℃ under the action of a nickel-iron bimetallic catalyst. The method is carried out in a fixed bed reactor, and paraxylene and toluene are obtained by injecting the catalyst through a high-pressure flow pump or passing the catalyst through a catalyst bed layer under the sweeping of hydrogen gas. The process has simple reaction process and high selectivity of target products, and the substrate can be obtained by carrying out Diels-Alder reaction on isoprene and acrolein. The raw materials of isoprene and acrolein can be obtained by converting biomass resources, so the raw materials have the characteristic of being renewable. In addition, the catalyst used in the reaction is a nickel-iron bimetallic catalyst, which is cheap and easy to obtain, and has high selectivity on the product. The method generates a small amount of toluene as a byproduct, and can generate benzene and C8 aromatic hydrocarbon through disproportionation or transalkylation of aromatic hydrocarbon of C9 or above (toluene disproportionation and transalkylation for short), thereby being an effective process route for increasing the yield of p-xylene.
Advantageous effects
(1) The synthetic method has the advantages of short path, simple reaction process, completion by two-step reaction, and high selectivity of the target product, which can reach 93%.
(2) The substrate 4-methyl-3-cyclohexene formaldehyde can be efficiently synthesized by the Diels-Alder reaction of bio-based isoprene and acrolein (ChemSusChem,2016,9: 3434-3440). Isoprene can be produced by fermentation of natural lignocellulose resources (WO/2013/149192.), acrolein can be prepared by dehydration of biodiesel byproduct glycerol (Green Chemistry,2007,9(10),1130-1136.), and the raw materials are renewable.
(3) The nickel-iron bimetal used in the reaction is easy to synthesize and good in performance, the decarbonylation capacity of nickel is improved by adding the iron element, so that the 4-methyl-3-cyclohexene can be catalyzed to be converted into the p-xylene, the needed nickel nitrate and ferric nitrate are cheap to purchase, and the cost can be saved.
Detailed Description
Example 1
(1)1％Ni/Al2O3The preparation of (1): all supported catalysts were prepared by wet impregnation, 1.49g Ni (NO)3)3.6H2Dissolving O in 30g of pure water, stirring uniformly, and adding 30g of alumina (20-40 meshes, the surface area is more than or equal to 200 m)2G, pore volume is more than or equal to 0.75m3/g) soaking in the solution, standing in an ultrasonic machine (100Hz) for 30min, drying at 80 deg.C for 12h, drying at 100 deg.C for 4h, and standing;
(2)1％Ni1％Fe/Al2O3preparation of bimetallic catalyst: 0.36g of iron nitrate nonahydrate is dissolved in 6.5g of pure water, and after uniform stirring, 5g of the prepared 1% wtNi/Al2O3Soaking in the ferric nitrate solution, ultrasonic treating for 30min in an ultrasonic machine (100Hz), standing for 12h, baking at 80 deg.C for 12h, and baking at 100 deg.C for 4 h. Calcining at 500 deg.C in air for 4h, reducing at 550 deg.C in hydrogen atmosphere for 1h, and controlling hydrogen flow rate at 120 mL/min. After the reduction, the temperature is reduced to room temperature, and 5 percent volO is adopted2/N2Passivating for 4 hours in the mixed gas to obtain 1 percent of Ni1 percent of Fe/Al2O3A bimetallic catalyst.
Comparative example 1
1％Ni/Al2O3As comparative example 1, the preparation was carried out in the same manner as in example 1 (1)
Examples 2 to 7
Varying the amount of ferric nitrate nonahydrate added in example 1 resulted in catalysts of different iron loadings, which were reported as 1% Ni 3% Fe/Al, respectively2O3、1％Ni/5％Fe/Al2O3、1％Ni7％Fe/Al2O3、1％Ni10％Fe/Al2O3、1％Ni12％Fe/Al2O3、1％Ni15％Fe/Al2O3。
Example 8
The catalysts prepared in examples 1 to 7 and comparative example 1 were subjected to a performance test:
a tubular reactor (inner diameter 10mm) was charged with 0.25g of the solid catalyst (20-40 mesh) obtained in examples 1 to 7 or comparative example 1, heated to 550 ℃ and charged with H2The carrier gas was purged for one hour to activate the catalyst. Then adding 200mg/mL of reaction raw material (n-hexane as solvent) into a raw material bottle, heating to 200 deg.C, injecting the reaction raw material solution into a gasification chamber (flow rate: 2.5mL/H) with a high-pressure constant flow pump, gasifying in the gasification chamber (gasification temperature 150 deg.C), and introducing into a reaction vessel with a hydrogen supply2Introducing reaction raw materials into a tubular reactor for carrier gas to ensure that the reaction raw materials circulate in a catalyst layer to react, wherein the flow rate of the carrier gas is controlled to be 10ml/min, the tail part of the reactor is connected with a collecting bottle, and the collecting bottle is cooled by ice water to ensure that a product is completely collected; the conversion and product yield were quantitatively calculated by combining GC-MS, and the catalyst medium species and reaction conditions (reaction temperature and carrier gas flow rate) were varied to obtain different performance results, which are shown in Table 1
TABLE 1 results of catalytic reaction of p-methylcyclohexene carboxaldehyde with different catalysts in fixed bed reactor
As can be seen from Table 1, the selectivity to p-xylene increases with the iron content on the catalyst at 200 deg.CIncreasing, 1% Pd 15% Fe/Al2O3The selectivity to p-xylene ladies is the best, and can reach 79%. 1% Pd 15% Fe is used as a catalyst, the reaction temperature is optimized at 150-250 ℃, the effect is best at 250 ℃, and the yield of the p-xylene can reach 93%.
Example 9
With 1% Ni 15% Fe/Al2O3The catalyst was used at a temperature of 250 ℃ and the concentrations of the starting materials were 50mg/mL, 100mg/mL, 200mg/mL and 500mg/mL, respectively, and the reaction results were as in example 8 and are shown in Table 2
Example 10
With 1% Ni 15% Fe/Al2O3The catalyst was used at 250 ℃ in the presence of 1, 4-dioxane and N-alkylpyrrolidone as solvents, and the reaction conditions were the same as in example 8, and the results are shown in Table 2.
TABLE 2 reactivity of catalyst reactions in different solvents and concentrations
Comparative example 2
1％Pd1％Ir/Al2O3(ii) a The production method is described in patent document 20141072727249.2.
Comparative example 3
30％W2C/AC: the preparation method is described in patent document CN 106883091A.
Comparative example 4
1％Pd10％Fe/Al2O3: preparing 6mL of aqueous solution from 6mL of 10mg/mL palladium nitrate solution and 3.6g of ferric nitrate nonahydrate, adding 6g of alumina carrier, soaking for 5 hours, drying at 80 ℃ for 12 hours, roasting at 450 ℃ for 4 hours, cooling, reducing at 350 ℃, reducing to room temperature after reduction, and adopting 5% volO2/N2Passivating for 4h in the mixed gas to obtain 1 percent Pd10 percent Fe/Al2O3A catalyst.
Comparative example 5
15％Fe/Al2O3The preparation of (1): 5.4g of nonawater and ferric nitrate were dissolved in6.5g of water, placing in an ultrasonic machine (100Hz) for more than 30min, standing for 12h, drying at 80 ℃ for 12h, and drying at 100 ℃ for 4 h. Calcining at 500 deg.C in air for 4h, reducing at 550 deg.C in hydrogen atmosphere for 1h, and controlling hydrogen flow rate at 120 mL/min. After the reduction, the temperature is reduced to room temperature, and 5 percent volO is adopted2/N2Passivating for 4 hours in the mixed gas to obtain 15 percent Fe/Al2O3A catalyst.
Example 11
The catalysts obtained in example 7 and comparative examples 1 to 5 were subjected to performance tests under the same conditions as in example 7 except that the kinds of the catalysts were changed and the reaction results are shown in Table 3.
Table 3 compares the activity of different catalysts
The invention has simple reaction process in the process and high selectivity of target products, and the substrate can be obtained by one-step reaction by taking isoprene and acrolein which are derived from biomass resources as raw materials, thereby providing a new method for directly preparing aromatic chemicals from biomass. As can be seen from Table 3, the nickel-iron bimetallic catalyst is used for catalyzing the conversion of 4-methyl-3-cyclohexene formaldehyde to prepare p-xylene, has better performance, and under the optimized condition, 1 percent of Ni15 percent of Fe/Al2O3The yield of p-xylene catalytically converted by the catalyst is up to 93%.
Claims (8)
1. A method for preparing p-xylene by catalyzing 4-methyl-3-cyclohexene formaldehyde to convert by a nickel-iron bimetallic catalyst is characterized in that 4-methyl-3-cyclohexene formaldehyde solution is blown from a raw material bottle by carrier gas or directly injected into a gas-solid phase reactor filled with the nickel-iron bimetallic catalyst by a high-pressure flow pump and then is put into a 250 th reactoroC, reacting to generate p-xylene; the catalyst is a supported nickel-iron bimetallic catalyst and comprises an active component and a carrier; the active component is a nickel-iron bimetal; in the nickel-iron bimetallic catalyst, the content of nickel is 1wt%, and the content of iron is 15 wt%;
the solvent for dissolving the 4-methyl-3-cyclohexene formaldehyde solution is n-hexane;
the concentration of the 4-methyl-3-cyclohexene formaldehyde in the solvent is 50-200 mg/mL; the flow rate of the carrier gas was 10 mL/min.
2. The method of claim 1, wherein: the carrier gas is nitrogen, hydrogen or helium.
3. The method of claim 2, wherein: the carrier gas is hydrogen.
4. The method of claim 1, wherein: the carrier is Al2O3The specific surface area of the carrier is more than or equal to 200m2G, pore volume is more than or equal to 0.75m3/g。
5. The method of claim 1, wherein: the 4-methyl-3-cyclohexene carboxaldehyde solution was heated to 150 deg.CoAnd C, transferring the mixture into a gas-solid phase reactor by a carrier gas to carry out reaction.
6. The method of claim 1, wherein: and the 4-methyl-3-cyclohexene formaldehyde solution is injected into a gas-solid phase reactor for reaction through a high-pressure constant-flow pump.
7. The method of claim 1, wherein: the pressure of the reaction is 0.1MPa-0.2 MPa.
8. The method of claim 1, wherein: the reaction product is led out from the gas-solid phase reactor and then is collected by a cooler, and the temperature of the cooler is controlled to be-10 ℃ by an ice salt bathoC is below.
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| CN104010996A (en) * | 2012-01-26 | 2014-08-27 | 东丽株式会社 | Method for producing p-xylene and/or p-tolualdehyde |
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| CN105712817A (en) * | 2014-12-03 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for selective preparation of p-xylene and toluene from p-methylcyclohexene carboxaldehyde |
| CN106883089A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of 4- methyl -3- hexamethylenes cyclohexene carboxaldehyde synthesizes the method for toluene |
| CN106883091A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of method by 4- methyl -3- hexamethylene cyclohexene carboxaldehyde selectivity synthesis paraxylene |
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| CN104010996A (en) * | 2012-01-26 | 2014-08-27 | 东丽株式会社 | Method for producing p-xylene and/or p-tolualdehyde |
| FR3028854A1 (en) * | 2014-11-25 | 2016-05-27 | Ifp Energies Now | NOVEL METHODS OF OBTAINING P-TOLUIC ACID AND ITS DERIVATIVES |
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