CN112390700B - Ethylbenzene dehydrogenation method - Google Patents
Ethylbenzene dehydrogenation method Download PDFInfo
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- CN112390700B CN112390700B CN201910739798.4A CN201910739798A CN112390700B CN 112390700 B CN112390700 B CN 112390700B CN 201910739798 A CN201910739798 A CN 201910739798A CN 112390700 B CN112390700 B CN 112390700B
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 136
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 92
- DBQBWZSDXNFYJI-UHFFFAOYSA-N [B].[N].[P] Chemical compound [B].[N].[P] DBQBWZSDXNFYJI-UHFFFAOYSA-N 0.000 claims abstract description 35
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- 229910052582 BN Inorganic materials 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
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- 239000000203 mixture Substances 0.000 claims description 31
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- 239000011574 phosphorus Substances 0.000 claims description 30
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of synthesis, and particularly discloses an ethylbenzene dehydrogenation method, which comprises the steps of carrying out dehydrogenation reaction on ethylbenzene under the catalysis of a boron-nitrogen-phosphorus catalyst to prepare styrene; the boron-nitrogen-phosphorus catalyst is a boron nitride two-dimensional material modified with P ═ O and P-OH. The invention is characterized in that the boron nitride two-dimensional material modified with P ═ O and P-OH is used as a dehydrogenation catalyst of ethylbenzene. The inventor innovatively finds that the catalyst can show excellent high temperature resistance, high activity, high stability and good anti-carbon deposition capability in ethylbenzene dehydrogenation reaction, can effectively improve the ethylbenzene conversion rate, promotes the styrene selectivity, improves the reaction activity, and can also effectively improve the catalytic stability.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to an ethylbenzene dehydrogenation method.
Background
Dehydrogenation of hydrocarbons is one of the most challenging issues in the petrochemical industry, and is characterized by a large limitation on the conversion of dehydrogenation due to thermodynamic equilibrium. Styrene is one of the most important basic raw materials in the modern petrochemical industry, and is also an important monomer for synthesizing various high molecular materials, such as polystyrene and styrene-butadiene rubber. In recent years, various new materials using styrene as a raw material have been emerging, and the market demand for styrene has been increasing year by year. The relevant data shows that domestic styrene production capacity will exceed 1000 million tons per year by 2020. But according to the increase speed estimation of the styrene demand of the current domestic market, the gap of the styrene demand of the domestic market still exceeds 200 ten thousand tons per year at that time, which means that the research and development of the catalyst for preparing styrene by ethylbenzene dehydrogenation with high performance, low cost and low energy consumption has important significance.
The Lummus/Monsanto/UOP (LMU) process for producing styrene by using potassium-containing iron oxide as catalyst and catalyzing ethylbenzene dehydrogenation under the condition of steam oxygen supply is the most widely applied styrene production technology in the world at present, the technical research has been over 70 years of history so far, the corresponding research result is also widely recognized, and the styrene produced by adopting the process accounts for more than 90 percent of the total styrene production amount in the world.
In the actual production process, the reaction for preparing styrene by ethylbenzene dehydrogenation is considered to be a strong endothermic reaction with the increased molecular number, the limitation of thermodynamic equilibrium is large, and the reaction conversion rate is favorably improved under the conditions of low pressure and high temperature. The reaction temperature of the LMU process is 600-650 ℃, and a large amount of water vapor (the water/hydrocarbon ratio is 7-15) needs to be introduced to delay the coking of the catalyst, dilute the reaction system and improve the equilibrium conversion rate. The large consumption of the water vapor causes huge energy consumption in the whole production process. Under the background, an energy-saving catalyst with high activity, high selectivity and stability is found, and the catalyst which can be operated under the condition of no water or low water/hydrocarbon ratio has important significance for saving energy and reducing consumption in the production process of styrene.
At present, the energy-saving catalyst suitable for low water/hydrocarbon ratio reported in literature and patent is mainly to add elements such as chromium, cerium, manganese and the like into the existing potassium-containing iron oxide catalyst to optimize the composition of the catalyst. Such as: CN106423187A, CN106423240A, CN105312059A and CN 105749934A. In particular, the catalyst reported in patent CN105749934A can be used at a relatively low water/hydrocarbon (1.2-2.0) ratio, but the problem of high energy consumption when introducing water vapor still exists, and the introduction of chromium, cerium and manganese elements in the above patent increases the cost of the catalyst and the risk of environmental pollution.
In recent years, new non-metallic catalysts, such as nanodiamond, boron nitride, carbon nitride, and boron carbide, have attracted the attention of researchers. Boron carbide (CN109126843A), nanodiamond (ChemUSchem Communications,2016,9, 662-666) mainly reported by Shenyang metal of Chinese academy of sciences; the nanodiamond/carbon nitride (Applied Catalysis A: General,571 (2019)) 82-88, Materials Chemistry A,2014,2, 13442-13451 reported by university of great connecting engineering shows higher activity and selectivity under the condition of anhydrous and anaerobic direct dehydrogenation of ethylbenzene or aerobic dehydrogenation; some materials, such as commercial boron carbide, exhibit higher stability but lower activity.
The work greatly expands the application of the nonmetal catalyst in ethylbenzene dehydrogenation, and particularly researches on the preparation of styrene catalyst by direct dehydrogenation under anhydrous condition. However, nitrogen-doped carbon materials are easy to decompose at high temperature, so that most of the catalysts are limited to be applied below 550 ℃, so that the activity and the stability of the catalysts are not ideal. In addition, compared with anhydrous anaerobic dehydrogenation, anhydrous aerobic dehydrogenation is easy to generate more byproduct carbon dioxide, so that the development of a non-metal catalyst which is suitable for anhydrous conditions (especially anhydrous and anaerobic), high temperature resistant, excellent in performance and simple in preparation process is still the focus of current research.
Disclosure of Invention
The invention provides an ethylbenzene dehydrogenation method, aiming at solving the problems of energy consumption caused by large steam consumption when the existing potassium-containing iron oxide catalyst is used for preparing styrene by ethylbenzene dehydrogenation and low using temperature, activity and stability of a nonmetal catalyst.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
an ethylbenzene dehydrogenation method, ethylbenzene is subjected to dehydrogenation reaction under the catalysis of a boron nitrogen phosphorus catalyst (also called a phosphorus modified boron nitride catalyst or simply called a catalyst) to prepare styrene;
the boron-nitrogen-phosphorus catalyst is a boron nitride two-dimensional material modified with P ═ O and P-OH.
The invention is characterized in that the boron nitride two-dimensional material modified with P ═ O and P-OH is used as a dehydrogenation catalyst of ethylbenzene. The inventor innovatively finds that the catalyst can show excellent high temperature resistance, high activity, high stability and good anti-carbon deposition capability in ethylbenzene dehydrogenation reaction, can effectively improve the ethylbenzene conversion rate, promotes the styrene selectivity, improves the reaction activity, and can also effectively improve the catalytic stability.
Preferably, the boron nitrogen phosphorus catalyst two-dimensional material is in a nano lamellar structure. The interlayer spacing is about 2-3 nm, the thickness of the single-layer lamella is about 1.2-1.5 nm, and the specific surface area is 140-260 m2/g。
Preferably, the method comprises the following steps: in the boron-nitrogen-phosphorus catalyst, the molar ratio of boron element to nitrogen element is 1: 24 to 32.
The invention further innovatively discovers that the catalytic performance can be further improved by controlling the element molar ratio of boron to phosphorus in the catalyst on the basis of initiatively utilizing the boron-nitrogen-phosphorus catalyst for catalyzing ethylbenzene dehydrogenation.
Preferably, in the boron-nitrogen-phosphorus catalyst, the element molar ratio of boron to phosphorus is 1: 0.9-1.4; preferably 1: 1.1-1.2. The inventor researches and unexpectedly finds that the catalytic activity, selectivity and stability can be further improved by controlling the B/P ratio.
The invention also provides a preparation method of the boron nitrogen phosphorus catalyst with excellent catalytic performance in ethylbenzene dehydrogenation, which is characterized in that raw material aqueous solution containing a boron source, a nitrogen source and a phosphorus source is recrystallized, and then a recrystallized product is dried and roasted in an ammonia atmosphere to obtain the boron nitrogen phosphorus catalyst;
the phosphorus source is one of hydroxyl ethylidene diphosphoric acid monohydrate, hexachlorotriphosphazene and ammonium dihydrogen phosphate;
in the raw material water solution, the element molar ratio of total boron to total phosphorus is 1: 0.9-1.4; preferably 1: 1.1-1.2;
the element molar ratio of total boron to total nitrogen is 1: 24-32;
the roasting temperature is 750-850 ℃.
The research of the inventor finds that the phosphorus modification form of the boron nitride two-dimensional material can be regulated and controlled by strictly controlling the phosphorus source type, the B/P ratio and the roasting temperature, and the material with excellent catalytic performance in ethylbenzene dehydrogenation can be unexpectedly prepared. Studies have also found that without the use of the phosphorus source, and without control at the required B/P ratio and firing temperature, uniform sizing affects P ═ O and POH modification, and thus catalytic performance.
Preferably, the boron source is selected from one of boric acid and boron oxide.
Preferably, the nitrogen source is selected from one of urea, dicyanodiamine, and melamine.
Preferably, the temperature of recrystallization is 40-90 ℃; the vacuum drying temperature of the recrystallized product is 50-80 ℃, and the drying time is 10-20 h.
Preferably, the introduction amount of ammonia in the ammonia-containing atmosphere is 40-60 ml/min.
Preferably, the roasting temperature is 800-850 ℃; further preferably 800 to 820 ℃.
Preferably, the roasting time is 2-5 h, and the temperature rise rate in the roasting temperature rise process is 1-5 ℃/min.
In the present invention, the dehydrogenation reaction may be carried out in the presence or absence of water, and is more preferably carried out in the absence of water. The anhydrous state refers to the state without external water and water vapor.
Preferably, the method comprises the following steps: the dehydrogenation reaction is carried out in an oxygen-free atmosphere or an oxygen-free atmosphere.
Preferably, the method comprises the following steps: physically mixing the boron-nitrogen-phosphorus catalyst with a catalyst diluent, and filling the mixture into a catalytic bed. The catalyst diluent is, for example, quartz sand.
In the present invention, there is no requirement for the amount of catalyst diluent, such as quartz sand.
Preferably, ethylbenzene is mixed into a carrier gas and flows through a catalyst bed loaded with the boron-nitrogen-phosphorus catalyst to perform gas-solid dehydrogenation reaction.
In the present invention, ethylbenzene may be mixed into the carrier gas by conventional methods, for example, by bubbling styrene through the carrier gas.
Preferably, the carrier gas is a water vapor-free oxygen-containing gas or an oxygen-free gas, for example, the carrier gas may be nitrogen, argon, helium, or the like.
In the carrier gas carrying the ethylbenzene, the volume fraction of the ethylbenzene is 0.495-16.512%; wherein the volume ratio of the ethylbenzene to the oxygen is 1: 0-20; preferably 1 (0.5-20).
The airspeed of the carrier gas carrying ethylbenzene is 600-4800 h-1。
The present inventors have found that, by using the above-described catalyst in an innovative manner, the catalytic performance of the catalyst can be further exhibited by further controlling the dehydrogenation reaction temperature.
Preferably, the temperature of the dehydrogenation reaction is 500-700 ℃; preferably 550-650 ℃; more preferably 600 to 650 ℃. Different from the existing nonmetal catalyst, the catalyst provided by the invention has better high temperature resistance, is higher in applicable temperature, and can also show better catalytic activity at the preferred temperature.
The principle is as follows:
the active sites of the non-metal catalyst in the ethylbenzene dehydrogenation reaction are mostly considered to be C ═ O groups or B — OH groups present on the surfaces of carbon materials and boron nitride materials. In the preparation process of the non-metal boron nitrogen phosphorus catalyst, the selection of the phosphorus-containing precursor, the molar ratio of the boron element to the phosphorus element and the difference of the roasting temperature have great influence on the catalytic performance of the non-metal boron nitrogen phosphorus catalyst. The microstructure of the nonmetal boron nitrogen phosphorus catalyst prepared by the method is found by combining various characterization means as follows: the average thickness is 1.2-1.5 nanometers, and the specific surface area is 140-260 m2(ii) a sheet material per gram (see figures 1, 2). The boron atoms and the nitrogen atoms are alternately arranged, are in a planar annular hexagon and are the same as the molecular skeleton of the hexagonal boron nitride; the phosphorus atom is present in the catalyst mainly in a manner of covalent bonding of the substituted skeleton boron atom and the defect site to form N3P-OH group and N2P ═ O group (see fig. 3) to modulate the performance of the catalyst. The phosphorus-containing precursor has different combination modes of phosphorus element and boron-nitrogen skeleton, so that the groups formed in the modification process of phosphorus are different, and the method mainly comprises the following steps: p ═ O, P-OH, N-P ═ N. Later experimental investigation revealed that the main groups affecting the catalyst activity were P ═ O and P — OH groups.
Has the advantages that:
1. the invention initiatively adopts the phosphorus-modified boron nitride two-dimensional material as the ethylbenzene dehydrogenation catalyst, and the catalyst is found to have unexpectedly excellent catalytic activity, catalytic selectivity and stability in ethylbenzene dehydrogenation;
2. the invention further researches and discovers that controlling the B/P ratio of the catalyst is helpful for further improving the catalytic activity of the catalyst in ethylbenzene dehydrogenation.
3. By controlling the phosphorus source type, the B/P ratio and the roasting temperature in the preparation process of the catalyst, the method is beneficial to regulating and controlling the phosphorus modification form and preparing the catalyst with excellent catalytic performance in ethylbenzene dehydrogenation. In addition, the prepared catalyst has good structural stability and good carbon deposition resistance, and can meet the production technical requirements of different conditions.
4. With the use of the inventive catalyst, a direct conversion of ethylbenzene without water can be achieved.
5. With the use of the inventive catalyst, good catalysis at temperatures above 550 ℃ can be achieved.
6. Under the use of the innovative catalyst, the dehydrogenation reaction temperature is further controlled in a synergistic manner, which contributes to further improvement of the catalytic performance.
7. Researches show that the initial conversion rate of the ethylbenzene can reach more than 70%, the selectivity of the styrene is 90%, and the stability is more than 20 hours.
8. Compared with potassium-containing iron oxide catalysts and non-metallic carbon catalysts, the boron-nitrogen-phosphorus catalyst provided by the invention has the advantages of high temperature resistance, strong carbon deposition resistance, simple preparation process and no metal pollution, and has a good industrial application prospect.
Description of the drawings:
FIG. 1: high Resolution Transmission Electron Microscopy (HRTEM) image of boron nitrogen phosphorus catalyst (BNP-HEDP-1.2) catalyst.
FIG. 2: atomic Force Microscope (AFM) picture of boron nitrogen phosphorus catalyst (BNP-HEDP-1.2) catalyst.
FIG. 3: x-ray photoelectron spectroscopy (XPS) full spectra (a) and P spectra (b) of boron nitrogen phosphorus catalyst (BNP-HEDP-1.2).
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Weighing 13.96g of commercially available urea and 0.6g of boric acid, adding 1.40g of hydroxyethylidene diphosphonic acid monohydrate (the molar ratio of boron element to phosphorus element is 1: 1.2), adding 30ml of distilled water, stirring for dissolving, then carrying out recrystallization operation on a beaker filled with a precursor-containing solution under the conditions of 80 ℃ oil bath and stirring at 300rpm/min until no obvious moisture exists, and then transferring the obtained white recrystallized product into a 50 ℃ vacuum drying oven for further drying for 12 hours. Grinding the dried recrystallization product into powder, loading the powder into a corundum ark, placing the corundum ark in a tubular furnace, introducing 60ml/min of ammonia gas to provide a roasting atmosphere, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min, roasting the mixture for 3 hours, and then naturally cooling the mixture to room temperature under the protection of ammonia gas to obtain the boron nitrogen phosphorus catalyst, which is recorded as BNP-HEDP-1.2.
The test method of the catalyst performance is as follows: 50mg of BNP-HEDP-1.2 catalyst is added into 2ml of quartz sand with the granularity of 40-60 meshes for dilution, the diluted BNP-HEDP-1.2 catalyst is placed into a fixed bed quartz reaction tube with the diameter of phi 8mm, and two ends of a catalyst bed layer are blocked by a small amount of quartz cotton. An inert gas atmosphere was provided by introducing 20ml/min of nitrogen gas. Under the protection of nitrogen, the temperature is raised to 600 ℃ at the speed of 4 ℃/min, the catalyst is pre-activated for 30min after being stabilized, and then mixed raw material gas with the volume fraction of 2.8 percent of ethylbenzene is introduced at the flow rate of 20ml/min for 20h of continuous reaction. The reaction product was collected with 0 ℃ ethanol and analyzed for composition by Shimadzu GC-2010Plus gas chromatograph, model RTX-5 column, FID detector. The initial ethylbenzene conversion rate is 62.42%, the styrene selectivity is 93.54%, and the styrene generation amount realized in unit time on the corresponding unit catalyst is 17.62 mmol/(g.h), and the stability can be realized for more than 20 hours.
Example 2
Weighing 13.96g of commercially available urea and 0.6g of boric acid, adding 1.63g of hydroxyethylidene diphosphonic acid monohydrate (the molar ratio of boron element to phosphorus element is 1: 1.4), adding 30ml of distilled water, stirring for dissolving, then carrying out recrystallization operation on a beaker filled with a precursor-containing solution under the conditions of 80 ℃ oil bath and stirring at 300rpm/min until no obvious moisture exists, and then transferring the obtained white recrystallized product into a 50 ℃ vacuum drying oven for further drying for 12 hours. Grinding the dried recrystallization product into powder, loading the powder into a corundum ark, placing the corundum ark in a tubular furnace, introducing 60ml/min of ammonia gas to provide a roasting atmosphere, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min, roasting the mixture for 3 hours, and then naturally cooling the mixture to room temperature under the protection of ammonia gas to obtain the boron nitrogen phosphorus catalyst, which is recorded as BNP-HEDP-1.4.
The catalyst performance test method of example 1 was used to determine that the catalyst performance was: the initial ethylbenzene conversion rate is 48.53%, the styrene selectivity is 87.89%, and the styrene generation amount in unit time on the corresponding unit catalyst is 12.87 mmol/(g.h), and the stability can be maintained for more than 20 hours.
Example 3
Weighing 13.96g of commercially available urea and 0.6g of boric acid, adding 1.36g of ammonium dihydrogen phosphate (the molar ratio of boron element to phosphorus element is 1: 1.2), adding 30ml of distilled water, stirring for dissolving, then carrying out recrystallization operation on a beaker filled with a precursor-containing solution under the conditions of 80 ℃ oil bath and stirring at 300rpm/min until no obvious moisture exists, and then transferring the obtained white recrystallized product into a 50 ℃ vacuum drying oven for further drying for 12 hours. Grinding the dried recrystallization product into powder, loading the powder into a corundum ark, placing the corundum ark in a tubular furnace, introducing 60ml/min ammonia gas to provide roasting atmosphere, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min, roasting the mixture for 3 hours, and naturally cooling the mixture to room temperature under the protection of ammonia gas to obtain the boron nitrogen phosphorus catalyst, namely the BNP-NH catalyst4H2PO4-1.2。
The catalyst performance test method of example 1 was used to determine that the catalyst performance was: the initial ethylbenzene conversion rate is 42.66%, the styrene selectivity is 91.78%, and the styrene generation amount in unit time on the corresponding unit catalyst is 11.82 mmol/(g.h), and the stability can be realized for more than 20 hours.
Example 4
Weighing 13.96g of commercially available urea, 0.6g of boric acid and 1.40g of hydroxyethylidene diphosphonic acid monohydrate (the molar ratio of boron element to phosphorus element is 1: 1.2), adding 30ml of distilled water, stirring and dissolving, then carrying out recrystallization operation on a beaker filled with a precursor-containing solution under the conditions of 80 ℃ oil bath and stirring at 300rpm/min until no obvious moisture exists, and then transferring the obtained white recrystallized product into a 50 ℃ vacuum drying oven for further drying for 12 hours. Grinding the dried recrystallization product into powder, loading the powder into a corundum ark, placing the corundum ark in a tubular furnace, introducing 60ml/min of ammonia gas to provide roasting atmosphere, heating the mixture from room temperature to 850 ℃ at the heating rate of 5 ℃/min, roasting the mixture for 3 hours, and then naturally cooling the mixture to the room temperature under the protection of ammonia gas to obtain the boron nitrogen phosphorus catalyst, namely the BNP-HEDP-1.2-850.
The catalyst performance test method of example 1 was used to determine that the catalyst performance was: the initial ethylbenzene conversion rate is 58.22%, the styrene selectivity is 91.48%, and the styrene yield per unit time on the corresponding catalyst is 16.07 mmol/(g.h), which can be stabilized for more than 20 hours.
Example 5
The catalyst BNP-HEDP-1.2 from example 1 was reacted at a higher reaction temperature. The method specifically comprises the following steps: 50mg of BNP-HEDP-1.2 catalyst is added into 2ml of quartz sand with the granularity of 40-60 meshes for dilution, the diluted BNP-HEDP-1.2 catalyst is placed into a fixed bed quartz reaction tube with the diameter of phi 8mm, and two ends of a catalyst bed layer are blocked by a small amount of quartz cotton. An inert gas atmosphere was provided by introducing 20ml/min of nitrogen gas. Under the protection of nitrogen, the temperature is raised to 650 ℃ at the speed of 4 ℃/min, the catalyst is pre-activated for 30min after being stabilized, and then mixed raw material gas with the volume fraction of 2.8 percent of ethylbenzene is introduced at the flow rate of 20ml/min for 20h of continuous reaction. The reaction product was collected with 0 ℃ ethanol and analyzed for composition by Shimadzu GC-2010Plus gas chromatograph, model RTX-5 column, FID detector. The initial ethylbenzene conversion rate is 70.51%, the styrene selectivity is 88.35%, and the styrene generation amount per unit time on the corresponding unit catalyst is 18.80 mmol/(g.h), and the stability can be realized for more than 20 hours.
Example 6
Weighing 13.96g of commercially available urea and 0.6g of boric acid, adding 1.40g of hydroxyethylidene diphosphonic acid monohydrate (the molar ratio of boron element to phosphorus element is 1: 1.2), adding 30ml of distilled water, stirring for dissolving, then carrying out recrystallization operation on a beaker filled with a precursor-containing solution under the conditions of 80 ℃ oil bath and stirring at 300rpm/min until no obvious moisture exists, and then transferring the obtained white recrystallized product into a 50 ℃ vacuum drying oven for further drying for 12 hours. Grinding the dried recrystallization product into powder, loading the powder into a corundum ark, placing the corundum ark in a tubular furnace, introducing 60ml/min of ammonia gas to provide a roasting atmosphere, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min, roasting the mixture for 3 hours, and then naturally cooling the mixture to room temperature under the protection of ammonia gas to obtain the boron nitrogen phosphorus catalyst, which is recorded as BNP-HEDP-1.2.
The reaction was carried out under an aerobic condition by the catalyst performance test method in example 1. The method specifically comprises the following steps: 50mg of BNP-HEDP-1.2 catalyst is added into 2ml of quartz sand with the granularity of 40-60 meshes for dilution, the diluted BNP-HEDP-1.2 catalyst is placed into a fixed bed quartz reaction tube with the diameter of phi 8mm, and two ends of a catalyst bed layer are blocked by a small amount of quartz cotton. An inert gas atmosphere was provided by introducing 20ml/min of nitrogen gas. Under the protection of nitrogen, the temperature is raised to 550 ℃ at the speed of 4 ℃/min, and the catalyst is pre-activated after being stabilized for 30 min. Then mixed raw material gas with the volume fraction of 2.8 percent of ethylbenzene and the oxygen fraction of 2.8 percent is introduced at the flow rate of 20ml/min for continuous reaction for 20 hours. The reaction product was collected with 0 ℃ ethanol and analyzed for composition by Shimadzu GC-2010Plus gas chromatograph, model RTX-5 column, FID detector. The measured catalyst performance was: the initial ethylbenzene conversion rate is 45.02%, the styrene selectivity is 92.56%, and the styrene generation amount per unit time on the corresponding unit catalyst is 12.57 mmol/(g.h), and the stability can be realized for more than 20 hours.
Comparative example 1
Weighing 13.96g of commercially available urea and 0.6g of boric acid, adding 30ml of distilled water, stirring for dissolving, then carrying out recrystallization operation on a beaker filled with a precursor-containing solution under the conditions of 80 ℃ oil bath and 300rpm/min stirring until no obvious moisture exists, and then transferring the obtained white recrystallized product into a 50 ℃ vacuum drying oven for further drying for 12 hours. Grinding the dried recrystallization product into powder, loading the powder into a corundum ark, placing the corundum ark in a tubular furnace, introducing 60ml/min of ammonia gas to provide a roasting atmosphere, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min, roasting the mixture for 3 hours, and then naturally cooling the mixture to room temperature under the protection of ammonia gas to obtain the phosphorus-free doped (modified) boron nitride catalyst which is marked as BNP-0.
The catalyst performance test method of example 1 was used to determine that the catalyst performance was: the initial ethylbenzene conversion was 18.68% and the styrene selectivity was 68.65%, corresponding to a styrene production of 3.87 mmol/(g.h) per unit time on the catalyst.
Comparative example 2
Weighing 13.96g of commercially available urea and 0.6g of boric acid, adding 1.91g of phosphorous acid (the molar ratio of boron element to phosphorus element is 1: 1.2), adding 30ml of distilled water, stirring for dissolving, then carrying out recrystallization operation on a beaker filled with a precursor-containing solution under the conditions of 80 ℃ oil bath and stirring at 300rpm/min until no obvious moisture exists, and then transferring the obtained white recrystallized product into a 50 ℃ vacuum drying oven for further drying for 12 hours. Grinding the dried recrystallization product into powder, loading the powder into a corundum ark, placing the corundum ark in a tubular furnace, introducing 60ml/min ammonia gas to provide roasting atmosphere, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min, roasting the mixture for 3 hours, and naturally cooling the mixture to room temperature under the protection of ammonia gas to obtain the boron nitrogen phosphorus catalyst, namely the BNP-H3PO3-1.2。
The catalyst performance test method of example 1 was used to determine that the catalyst performance was: the initial ethylbenzene conversion was 22.36% and the styrene selectivity was 89.78%, corresponding to a styrene production of 6.06 mmol/(g.h) per unit time on the catalyst.
Comparative example 3
Weighing 13.96g of commercially available urea and 0.6g of boric acid, adding 0.23g of hydroxyethylidene diphosphonic acid monohydrate (the molar ratio of boron element to phosphorus element is 1: 0.2), adding 30ml of distilled water, stirring for dissolving, then carrying out recrystallization operation on a beaker filled with a precursor-containing solution under the conditions of 80 ℃ oil bath and stirring at 300rpm/min until no obvious moisture exists, and then transferring the obtained white recrystallized product into a 50 ℃ vacuum drying oven for further drying for 12 hours. Grinding the dried recrystallization product into powder, loading the powder into a corundum ark, placing the corundum ark in a tubular furnace, introducing 60ml/min of ammonia gas to provide a roasting atmosphere, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min, roasting the mixture for 3 hours, and then naturally cooling the mixture to room temperature under the protection of ammonia gas to obtain the boron nitrogen phosphorus catalyst, which is recorded as BNP-HEDP-0.2.
The catalyst performance test method of example 1 was used to determine that the catalyst performance was: the initial ethylbenzene conversion was 23.42% and the styrene selectivity was 67.19%, corresponding to a styrene production of 4.75 mmol/(g.h) per unit time per unit catalyst.
Comparative example 4
Weighing 50mg of the BASF iron potassium catalyst (with the granularity of 80-100 meshes and the same as that of the BNP catalyst) after grinding, adding 2ml of quartz sand with the granularity of 40-60 meshes for dilution, putting into a fixed bed quartz reaction tube with the diameter of 8mm, and plugging two ends of a catalyst bed layer by a small amount of quartz cotton. An inert gas atmosphere was provided by introducing 20ml/min of nitrogen gas. Under the protection of nitrogen, the temperature is raised to 600 ℃ at the speed of 4 ℃/min, the catalyst is pre-activated for 30min after being stabilized, and then mixed raw material gas with the volume fraction of 2.8 percent of ethylbenzene is introduced at the flow rate of 20ml/min for 20h of continuous reaction. The reaction product was collected with 0 ℃ ethanol and analyzed for composition by Shimadzu GC-2010Plus gas chromatograph, model RTX-5 column, FID detector.
The initial ethylbenzene conversion was 70.13%, the styrene selectivity was 93.19%, and the corresponding ethylbenzene conversion per unit of catalyst per unit of time was 19.72 mmol/(g.h); but the catalyst has poor stability, the ethylbenzene conversion rate is 20.62% when the reaction lasts for 10 hours, the styrene selectivity is 86.22%, and the ethylbenzene conversion amount realized in unit time on a corresponding unit catalyst is 5.36 mmol/(g.h); after 20h of reaction, the catalyst had deactivated, corresponding to an ethylbenzene conversion of only 12.18% and a styrene selectivity of 72.11%, the styrene yield per unit of catalyst achieved was 2.65 mmol/(g.h).
Comparative example 5
Referring to the published literature (angelwan Chemie,2017,129, 8343-9347), a carbon-doped (C-O, B-OH modified) boron nitride material (denoted as CBN) was prepared by calcining boric acid, urea and glucose as a boron source, a nitrogen source and a phosphorus source, respectively, at 1250 ℃ in an ammonia atmosphere, and the catalyst catalyzed an ethylbenzene dehydrogenation reaction at a reaction temperature of 500 ℃ under an aerobic condition (ethylbenzene: oxygen: 1:4) to achieve an initial ethylbenzene conversion of about 60% and a styrene selectivity of about 95%, corresponding to a styrene generation of 1.71 mmol/(g-h) per unit time per unit catalyst.
Claims (20)
1. An ethylbenzene dehydrogenation method is characterized in that: carrying out dehydrogenation reaction on ethylbenzene under the catalysis of a boron-nitrogen-phosphorus catalyst to prepare styrene; the boron-nitrogen-phosphorus catalyst is a boron nitride two-dimensional material modified with P ═ O and P-OH;
the phosphorus source is one of hydroxyl ethylidene diphosphoric acid monohydrate, hexachlorotriphosphazene and ammonium dihydrogen phosphate;
in the boron nitrogen phosphorus catalyst, the molar ratio of boron to phosphorus is 1: 0.9-1.4;
the roasting temperature is 750-850 ℃.
2. The ethylbenzene dehydrogenation process of claim 1, wherein: in the boron nitrogen phosphorus catalyst, the molar ratio of boron to phosphorus is 1: 1.1-1.2.
3. The ethylbenzene dehydrogenation process of claim 1, wherein: in the boron-nitrogen-phosphorus catalyst, the molar ratio of boron element to nitrogen element is 1: 24 to 32.
4. The ethylbenzene dehydrogenation process of claim 1, wherein: the boron nitrogen phosphorus catalyst material is of a nano lamellar structure, the interlayer spacing is 2-3 nm, the thickness of a single lamellar is 1.2-1.5 nm, and the specific surface area is 140-260 m2/g。
5. The ethylbenzene dehydrogenation process of claim 1, wherein: the boron nitrogen phosphorus catalyst is obtained by recrystallizing a raw material aqueous solution containing a boron source, a nitrogen source and a phosphorus source, and then drying and roasting a recrystallized product in an ammonia atmosphere;
in the raw material water solution, the element molar ratio of total boron to total phosphorus is 1: 0.9-1.4;
the element molar ratio of total boron to total nitrogen is 1: 24 to 32.
6. The ethylbenzene dehydrogenation process of claim 5, wherein: in the raw material water solution, the element molar ratio of total boron to total phosphorus is 1: 1.1-1.2.
7. The ethylbenzene dehydrogenation process of claim 5, wherein: the boron source is selected from one of boric acid and boron oxide;
the nitrogen source is selected from one of urea, dicyandiamide and melamine.
8. The ethylbenzene dehydrogenation process of claim 5, wherein: the recrystallization temperature is 40-90 ℃; the vacuum drying temperature of the recrystallized product is 50-80 ℃, and the drying time is 10-20 h.
9. The ethylbenzene dehydrogenation process of claim 5, wherein: the amount of ammonia gas introduced into the ammonia gas-containing atmosphere is 40 to 60 ml/min.
10. The ethylbenzene dehydrogenation process of claim 5, wherein: the roasting temperature is 800-850 ℃.
11. The ethylbenzene dehydrogenation process of claim 5, wherein: the roasting time is 2-5 h, and the temperature rise rate in the roasting temperature rise process is 1-5 ℃/min.
12. The ethylbenzene dehydrogenation process of claim 1, wherein: the dehydrogenation reaction is carried out under anhydrous conditions.
13. The ethylbenzene dehydrogenation process of claim 12, wherein: the dehydrogenation reaction is carried out in an oxygen-free atmosphere or an oxygen-free atmosphere.
14. The ethylbenzene dehydrogenation process of claim 12, wherein: physically mixing the boron-nitrogen-phosphorus catalyst with a catalyst diluent, and filling the mixture into a catalytic bed.
15. The ethylbenzene dehydrogenation process of claim 14, wherein: and mixing ethylbenzene with carrier gas, and then flowing through a catalytic bed loaded with the boron-nitrogen-phosphorus catalyst to perform dehydrogenation reaction.
16. The ethylbenzene dehydrogenation process of claim 15, wherein: the carrier gas is oxygen-containing gas without water vapor or oxygen-free gas.
17. The ethylbenzene dehydrogenation process of claim 15, wherein: in the carrier gas carrying the ethylbenzene, the volume fraction of the ethylbenzene is 0.495-16.512%; wherein the volume ratio of the ethylbenzene to the oxygen is 1: 0-20;
the airspeed of the carrier gas carrying ethylbenzene is 600-4800 h-1。
18. The ethylbenzene dehydrogenation process of claim 17, wherein: the volume ratio of the ethylbenzene to the oxygen is 1 (0.5-20).
19. The ethylbenzene dehydrogenation process of any one of claims 1-18, wherein: the temperature of the dehydrogenation reaction is 500-700 ℃.
20. The ethylbenzene dehydrogenation process of claim 19, wherein: the temperature of the dehydrogenation reaction is 550-650 ℃.
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