CN110015940B - Method for preparing toluene and methane by oxidative dehydrogenation of methylcyclohexane under carbon dioxide atmosphere - Google Patents

Method for preparing toluene and methane by oxidative dehydrogenation of methylcyclohexane under carbon dioxide atmosphere Download PDF

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CN110015940B
CN110015940B CN201910419334.5A CN201910419334A CN110015940B CN 110015940 B CN110015940 B CN 110015940B CN 201910419334 A CN201910419334 A CN 201910419334A CN 110015940 B CN110015940 B CN 110015940B
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methylcyclohexane
methane
carbon dioxide
toluene
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王延吉
孙颖
丁晓墅
王淑芳
赵新强
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Hebei University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • 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
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/367—Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
    • 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
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • 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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Abstract

The invention relates to a method for preparing toluene and methane by oxidizing methyl cyclohexane for dehydrogenation under carbon dioxide atmosphere. The method comprises the following steps: mixing methylcyclohexane and CO2Introducing the mixture into a reactor, and reacting the mixture to generate toluene and methane through a catalyst bed layer of an isothermal device under the conditions that the reaction temperature is 100-500 ℃ and the reaction pressure is 0.1-2 MPa; the carrier of the catalyst is gamma-Al2O3、TiO2、SiO2The catalyst comprises any one of mordenite, ZSM-5 and active carbon, wherein the active component of the catalyst is Ni, and the auxiliary agent is one or two of Pt and Ce. The invention has the function of promoting CO2The method has the characteristics of recycling, improving the conversion rate of carbon dioxide, reducing the risk of hydrogen transportation and having higher popularization value.

Description

Method for preparing toluene and methane by oxidative dehydrogenation of methylcyclohexane under carbon dioxide atmosphere
Technical Field
The invention relates to a method for preparing toluene and methane by oxidizing methylcyclohexane for dehydrogenation under a carbon dioxide atmosphere.
Background
CO2Is the main greenhouse gas in the atmosphere, CO2The emission is mainly from the combustion of fossil fuel, the consumption of fuel mainly comprising coal, petroleum and natural gas accounts for 85.5% of the global energy consumption in 2016, and the generated CO2The emission amount is up to 33432 Mt. Continuously increased carbon-based energy consumption to make CO in atmosphere2The concentration of the compound is continuously increased, which not only causes the global warming problem, but also induces a series of other ecological environment problems, such as acid rain, animal migration and the like, and draws wide attention of all countries in the world. In recent years, for CO2The emission reduction, the recovery and the resource utilization are more and more concerned, and CO is absorbed2The conversion into energy products can realize the recycling of carbon,has great significance for the fields of environment and energy. CO in industry2The recovery and resource utilization mainly comprises a capture recovery technology, such as CO2Chemical products of absorption method, adsorption separation method and membrane separation method, and CO2Conversion using techniques, e.g. with CO2The raw materials are subjected to catalytic hydrogenation to produce methane, methanol, formic acid, dimethyl ether and the like. CO22The transformation application technology shows strong attraction and has better development prospect, and the application technology accounts for CO at present240% of the technology is utilized. Wherein, CO2Hydromethanation of CO in comparison with reactions to form other hydrocarbons or alcohols2The methanation has high reaction speed, high conversion rate and high selectivity, and has obvious advantages in the aspect of reaction thermodynamics. CO22The synthesis of methane by hydromethanation can realize CO2Emission reduction can be realized, the method can also be used as an important natural gas supplement source, the problem of natural gas supply shortage is solved, and the method has a very wide development prospect.
CO2Methanation reaction means CO2And H2Reacting under certain temperature and pressure and the action of a catalyst to generate CH4And H2And (4) O. The reaction is shown in the following formula.
CO2+4H2→CH4+2H2OΔH＝-165kJ/mol
CO2The methanation reaction is a strongly exothermic reaction, and from the thermodynamic point of view, high temperatures are unfavorable for CO2The methanation reaction is restricted by thermodynamic equilibrium, so that the equilibrium is favorably carried out in the positive direction at low temperature; from a kinetic point of view, low temperatures reduce CO2The methanation reaction speed is generally within the reaction temperature range of 150-500 ℃ during experiments. In addition, CO2The methanation reaction is a strong exothermic reaction, and the catalyst is easy to sinter and deactivate in the reaction process. CO22Side reactions may also occur during methanation, and whether or not side reactions occur on different catalysts and the degree of reaction progress will be different. Therefore, it is desired to realize CO under low temperature conditions2High conversion and CH4High selectivity, the choice of catalyst is critical.
The hydrogen energy is used as a clean energy source, can relieve the environmental pollution caused by fossil energy, solves the shortage of fossil energy and relieves the pressure of sustainable development. The hydrogen energy system which can be completely accepted by the public comprises the steps of hydrogen preparation, storage, transportation and utilization, and the operation is smooth. However, hydrogen energy cannot be applied to various industries of the society on a large scale so far, and the fundamental reason is that the technical bottleneck exists in the storage link of hydrogen. When hydrogen is used as a fuel, it must be dispersible and intermittently used, and therefore must be capable of being stored and transported to a designated place over a period of time. The International energy agency stipulates that a practical hydrogen storage system must have a mass hydrogen storage density of up to 5 wt%, and also require a volumetric hydrogen storage density of greater than 40kg/m3。
Methylcyclohexane (MCH) is used at its high hydrogen storage density: the mass hydrogen storage density was 6.1 w%, and the volume hydrogen storage density was 47kg/m3Compared with the benzene which is a carcinogen generated by cyclohexane, the benzene derivative has higher safety and gradually attracts great attention; secondly, the methylcyclohexane is a chemical product for industrial large-scale production; moreover, the hydrogen storage of the methylcyclohexane is a cyclic reversible process, namely, the toluene-methylcyclohexane can be hydrogenated and dehydrogenated without damaging the main structure of the carbon ring, which is a reaction with insensitive structure, the C-H bond is broken without influencing the structure of the C-C framework, and the reaction is reversible. Meanwhile, the hydrogenation process is a Gibbs free energy reduction process, the absolute value is extremely large, and the thermodynamics is extremely favorable, namely the hydrogenation process is very easy to carry out; the dehydrogenation process is a strong endothermic reaction, so far, the method has the main defects that the dehydrogenation reaction is an endothermic reaction, the required reaction temperature is higher, and the energy consumed by the dehydrogenation process accounts for about 30 percent of the stored hydrogen energy.
Disclosure of Invention
The invention aims to provide a method for preparing toluene and methane by oxidizing methylcyclohexane for dehydrogenation under a carbon dioxide atmosphere aiming at the defects in the prior art. The method uses MCH as a high-quality hydrogen storage medium and MCH hydrogen storage as a circulating reversible process, and can be CO2Methanation provides a source of hydrogen. The method has CO promoting effect2Recovery and resources ofThe method has the characteristics of chemical utilization, improvement of carbon dioxide conversion rate and reduction of hydrogen transportation danger, and has high popularization value.
The technical scheme of the invention is as follows:
a method for preparing toluene and methane by oxidizing methylcyclohexane for dehydrogenation under a carbon dioxide atmosphere comprises the following steps:
mixing methylcyclohexane and CO2Introducing the mixture into a reactor, and reacting the mixture to generate toluene and methane through a catalyst bed layer of an isothermal device under the conditions that the reaction temperature is 100-500 ℃ and the reaction pressure is 0.1-2 MPa;
wherein the molar ratio is CO2MCH is 1:1 to 1: 10; MCH and CO2The mixed sample introduction volume space velocity is 100h-1～1000h-1；
The carrier of the catalyst is gamma-Al2O3、TiO2、SiO2The catalyst comprises any one of mordenite, ZSM-5 and active carbon, wherein the active component of the catalyst is Ni in percentage by weight, and the loading range is 0.5-50%; the auxiliary agent is one or two of Pt and Ce, and the loading range is 0-40%.
The catalyst is preferably specifically: support gamma-Al2O3、TiO2、SiO2And any one of the active carbon, the active component of the catalyst is Ni in percentage by weight, and the loading range is 1-40%; the auxiliary agent is one or two of Pt and Ce, and the loading range is 1-30%.
The reaction temperature is preferably 200-480 ℃.
The invention has the beneficial effects that:
1. the hydrogen source of the invention is not high-purity hydrogen, and the transportation process is safe, namely CO is provided by methyl cyclohexane dehydrogenation2The hydrogen source required by methanation is convenient to transport due to the liquid methylcyclohexane and reduces H2The risk of the transportation process. And can convert greenhouse gas CO into2And efficiently converted into more useful methane gas.
2. The catalyst is prepared by selecting the active composition of the catalyst, adding a proper auxiliary agent, and preferably adopting a reasonable loading processHigh activity, selectivity and stability, the process uses 20% Ni-1% Pt/gamma-Al2O3Catalyst, methylcyclohexane and CO at 350 deg.C and 0.6MPa2Under the condition that the molar ratio is 0.5, the single-pass conversion rate of the methylcyclohexane is 92.44%, and the selectivity of the toluene is 99.25%; CO22The conversion was 33.32% and the methane selectivity was 95.86%.
The invention is further illustrated by the following examples.
Detailed Description
The preparation method and the evaluation method of the catalyst used in the process are as follows:
pretreating different carriers according to different methods; weighing the metal active components according to the mass ratio, impregnating the carrier with a salt solution of metal oxide, and then impregnating at normal temperature, drying and roasting to obtain a catalyst precursor; reducing the obtained solid catalyst precursor in a reducing atmosphere of N2And H2Reducing the mixed gas at the temperature of 300-600 ℃.
The invention is used for the dehydrogenation reaction of the reverse water gas conversion coupling methylcyclohexane on an isothermal evaluation device, and the process is briefly described as follows: MCH is preheated and vaporized and then reacts with CO2The gas enters a catalytic bed for reaction after being mixed. The heating of the reactor is controlled by an automatic control instrument, the temperature precision is 1 ℃, the dehydrogenated product enters a condenser through a quencher, gas-liquid separation is carried out through a gas-liquid separator, a liquid-phase product is collected in a collecting bottle, a gas-phase product is emptied after being measured by a wet flowmeter, and sampling is carried out once per hour. The reaction temperature is 200-500 ℃, the pressure is 0.1-2 MPa, and MCH and CO are2The mixed sample introduction volume space velocity is 100h-1～1000h-1，CO2And the molar ratio of MCH is 1-10. Both the liquid and gaseous products produced by the reaction were analyzed by gas chromatography.
[ example 1 ]
10g of 20-40 mesh gamma-Al2O3The carrier was added to 16.8ml of chloroplatinic acid (H) at a concentration of 0.02g/ml2PtCl4·6H2O), 12.545g of nickel nitrate (Ni (NO)3)2·6H2O) in an aqueous solution, and immersing 0.Drying at 120 deg.C for 10 hr for 5 hr, calcining at 550 deg.C for 4 hr to obtain catalyst precursor, and calcining the precursor in N atmosphere2And H2The volume ratio is 1:1, the Ni-Pt/gamma-Al is prepared by reducing for 4 hours under the condition that the temperature is 450 DEG C2O3A catalyst. The mass fractions of Ni and Pt in the catalyst in the total catalyst are respectively 20 wt% and 1 wt%.
The new process for preparing toluene and methane by oxidizing methylcyclohexane for dehydrogenation under the atmosphere of carbon dioxide comprises the following steps: 3ml of catalyst were charged in a reactor having an internal diameter of 6mm and a length of 300mm under N2And (4) testing leakage under the condition that the pressure is 1MPa, smearing each interface with soap water, and if the air leakage is detected, inflating again until the air leakage is avoided. Then the temperature is raised to 450 ℃ in a flow ratio N2:H280ml/min while introducing N2And H2Reducing for 60min, cooling to 350 ℃, and purifying N2And H2(turning off N)2And H2Inlet valve, gas flow meter becomes 0, and is marked as empty). Then introducing CO at 100ml/min2CO was changed after setting the reactor pressure to 0.6MPa2The flow rate was 6ml/min (0.016mol/min) through the reactor and the pressure in the reactor was kept at 0.6MPa, the feed MCH was passed through the reactor via a precision metering plunger pump at 0.017ml/min (0.008mol/min) and MCH and CO2The mixed sample introduction volume space velocity is 240h-1。
Both the liquid and gaseous products produced by the reaction were analyzed by gas chromatography. The single-pass conversion of methylcyclohexane was 92.44%, the toluene selectivity was 99.25%, and the selectivity of by-products was: benzene (0.75%); CO22The conversion rate is 33.32 percent, the methane selectivity is 95.86 percent, and the selectivity of byproducts is O2(1.39%), CO (2.2%), ethane (0.5%).
The obtained product is subjected to gas-liquid separation by a condenser. Because the selectivity of the product is very high, the obtained liquid phase product separates the reaction product in a reduced pressure distillation mode to obtain products with high purity and different fractions; the obtained gas phase product can be separated by industrial methods such as a condensation method, a selective adsorption method, an absorption method and the like to obtain a high-purity gas product.
[ example 2 ]
10g of 20-40 mesh gamma-Al2O3The carrier was added to 15.8ml of chloroplatinic acid (H) at a concentration of 0.02g/ml2PtCl4·6H2O), 8.841g of nickel nitrate (Ni (NO)3)2·6H2O) water solution, soaking for 0.5 hour, drying at 120 ℃ for 10 hours, roasting at 550 ℃ for 4 hours to prepare a catalyst precursor, and then putting the solid catalyst precursor in the atmosphere of N2And H2The Ni-Pt/gamma-Al is prepared by reducing for 4 hours under the conditions of volume ratio of 80:80ml/min and temperature of 450 DEG C2O3A catalyst. The mass fractions of Ni and Pt in the catalyst in the total catalyst are respectively 15 wt% and 1 wt%.
The new process for preparing toluene and methane by oxidizing methylcyclohexane for dehydrogenation under the atmosphere of carbon dioxide comprises the following steps: the process flow and reaction process conditions were the same as in example 1. The single-pass conversion rate of the methylcyclohexane is 87.30 percent, and the selectivity of the toluene is 100 percent; CO22The conversion rate is 28.33 percent, the methane selectivity is 95.23 percent, and the selectivity of byproducts is O2(2.11%), CO (2.19%), ethane (0.47%).
[ example 3 ]
10g of 20-40 mesh gamma-Al2O3The carrier was added to 14.92ml of chloroplatinic acid (H) at a concentration of 0.02g/ml2PtCl4·6H2O), 5.5691g of nickel nitrate (Ni (NO)3)2·6H2O) water solution, soaking for 0.5 hour, drying at 120 ℃ for 10 hours, roasting at 550 ℃ for 4 hours to prepare a catalyst precursor, and then putting the solid catalyst precursor in the atmosphere of N2And H2The Ni-Pt/gamma-Al is prepared by reducing for 4 hours under the conditions of volume ratio of 80:80ml/min and temperature of 450 DEG C2O3A catalyst. The mass fractions of Ni and Pt in the catalyst in the total catalyst are respectively 10 wt% and 1 wt%.
The new process method for preparing toluene and methane by oxidizing methylcyclohexane for dehydrogenation under the atmosphere of carbon dioxide comprises the following steps: the process flow and reaction process conditions were the same as in example 1. The single-pass conversion rate of the methylcyclohexane is 91.65%, the selectivity of the toluene is 98.81%, and the selectivity of the byproduct is respectively as follows: tetrahydrofuran (0.19%), benzene (0.625%), 3-methyl-hexane (0.18%), m-xylene (0.195%); CO22The conversion rate is 29.10 percent, the methane selectivity is 91.01 percent, and the selectivity of byproducts is O2(1.58%), CO (6.24%), ethane (1.17%).
[ example 4 ]
10g of 20-40 mesh gamma-Al2O3The carrier was added to 14.92ml of chloroplatinic acid (H) at a concentration of 0.02g/ml2PtCl4·6H2O), 5.5691g of nickel nitrate (Ni (NO)3)2·6H2O) water solution, soaking for 0.5 hour, drying at 120 ℃ for 10 hours, roasting at 550 ℃ for 4 hours to prepare a catalyst precursor, and then putting the solid catalyst precursor in the atmosphere of N2And H2The Ni-Pt/gamma-Al is prepared by reducing for 4 hours under the conditions of volume ratio of 80:80ml/min and temperature of 450 DEG C2O3A catalyst. The mass fractions of Pt and Ni in the catalyst in the total catalyst are respectively 5 wt% and 1 wt%.
The new process for preparing toluene and methane by oxidizing methylcyclohexane for dehydrogenation under the atmosphere of carbon dioxide comprises the following steps: the process flow and reaction process conditions were the same as in example 1. The single-pass conversion rate of the methylcyclohexane is 81.22%, the selectivity of the toluene is 97.22%, and the selectivity of the by-product is respectively as follows: tetrahydrofuran (0.97%), benzene (1.13%), methylethylbenzene (0.234%), m-xylene (0.446%); CO22The conversion rate is 25.06 percent, the methane selectivity is 84.77 percent, and the selectivity of byproducts is O2(2.93%), CO (11.41%), ethane (0.89%).
[ example 5 ]
10g of 20-40 mesh gamma-Al2O3The support was added to 5.5691g of nickel nitrate (Ni (NO)3)2·6H2O), 14.92ml chloroplatinic acid (H) at a concentration of 0.02g/ml2PtCl4·6H2O), 4.75g of cerium nitrate (Ce (NO)3)3·6H2O) water solution, soaking for 0.5 hour, drying at 120 ℃ for 10 hours, roasting at 550 ℃ for 4 hours to prepare a catalyst precursor, and then putting the solid catalyst precursor in the atmosphere of N2And H2The Ni-Pt-Ce/gamma-Al is prepared by reducing for 4 hours under the conditions of volume ratio of 80:80ml/min and temperature of 450 DEG C2O3A catalyst. The mass fractions of Ni, Pt and Ce in the catalyst in the total catalyst are respectively 5 wt%, 1 wt% and 5 wt%.
The new process for preparing toluene and methane by oxidizing methylcyclohexane for dehydrogenation under the atmosphere of carbon dioxide comprises the following steps: the process flow and reaction process conditions were the same as in example 1. The single-pass conversion rate of the methylcyclohexane is 86.39%, the selectivity of the toluene is 99.45%, and the selectivity of the byproducts is respectively as follows: tetrahydrofuran (0.27%), benzene (0.28%); CO22The conversion rate is 24.95 percent, the methane selectivity is 90.81 percent, and the selectivity of byproducts is O2(1.02%), CO (7.98%), ethane (0.19%).
The invention is not the best known technology.

Claims (1)

1. A method for preparing toluene and methane by oxidizing methylcyclohexane for dehydrogenation under carbon dioxide atmosphere is characterized by comprising the following steps:
introducing methylcyclohexane and CO2 into a reactor, and reacting through a catalyst bed layer of an isothermal device under the conditions that the reaction temperature is 200-480 ℃ and the reaction pressure is 0.1-2 MPa to generate toluene and methane;
wherein the molar ratio of CO2 to methylcyclohexane =1: 1-1: 10; the mixed sample introduction volume space velocity of the methylcyclohexane and the CO2 is 100h < -1 > to 1000h < -1 >;
the carrier of the catalyst is gamma-Al 2O3, the active component of the catalyst is Ni in percentage by weight, and the loading range is 0.5-50%; the auxiliary agent is Pt or Ce, and the loading range is 1-40%.
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低碳烷烃CO2氧化脱氢催化剂的制备及其催化性能的研究;史雪君;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20100715(第07期);第B014-73页 *

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