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WO2020047902A1 - Procédé de préparation et utilisation de catalyseur à tamis moléculaire - Google Patents

Procédé de préparation et utilisation de catalyseur à tamis moléculaire Download PDF

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WO2020047902A1
WO2020047902A1 PCT/CN2018/106165 CN2018106165W WO2020047902A1 WO 2020047902 A1 WO2020047902 A1 WO 2020047902A1 CN 2018106165 W CN2018106165 W CN 2018106165W WO 2020047902 A1 WO2020047902 A1 WO 2020047902A1
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molecular sieve
sieve catalyst
preparing
zsm
water
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PCT/CN2018/106165
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Chinese (zh)
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苏雄
杨晓丽
黄延强
张涛
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中国科学院大连化学物理研究所
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/073—Ethylbenzene
    • 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
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • 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
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol

Definitions

  • the present application relates to a preparation method and application of a molecular sieve catalyst, and belongs to the field of materials.
  • Ethylbenzene is an important commercial derivative of benzene in the current chemical industry. It is mainly used for dehydrogenation to styrene, and it is also an important raw material for the production of polystyrene and ABS resin. In recent years, the market demand for ethylbenzene has shown a clear upward trend. However, the depletion of petroleum resources and the soaring oil prices have greatly increased the cost of ethylene alkylation. It has become a trend to seek new raw materials instead of ethylene to produce ethylbenzene.
  • ethanol can be produced not only through the petroleum route, but also from large-scale production of agricultural and sideline products and coal, which saves costs from the source of ethanol production and also provides more space for the choice of raw materials for ethylbenzene production.
  • Gas-phase alkylation of ethanol and benzene to ethylbenzene is based on low-cost renewable resources ethanol or coal-based ethanol.
  • the process is environmentally friendly. It not only optimizes the product structure of the chemical market, increases economic benefits, but also contributes to the national energy strategy. Deployment has long-term implications.
  • the ethanol to ethylbenzene process is a process in which ethanol and benzene undergo ethanol dehydration and benzene alkylation simultaneously in the reactor.
  • the catalyst used not only needs to meet the high dehydration selectivity and conversion of ethanol, but also has certain requirements for the catalytic efficiency of the alkylation of ethylene and benzene.
  • ZSM-5 molecular sieve has strong acidic sites and can effectively catalyze ethanol dehydration and benzene alkylation at the same time; and the large-scale preparation process of the molecular sieve is relatively mature and has become the main catalyst in the reaction industry.
  • Li Jianjun of Xiamen University uses NaOH solution to ream the ZSM-5 molecular sieve, which improves the stability of the molecular sieve and the selectivity of ethylbenzene (Journal of Xiamen University (Natural Edition), 2012, 51, 5, 882-887); Wen Ding et al.
  • Mg auxiliaries after treating ZSM-5 with alkali significantly increased the selectivity of ethylbenzene compared to the original parent molecular sieves (RSC Advances, 2014, 4, 50123-50129).
  • a method for preparing a molecular sieve catalyst has good reproducibility, generates less waste water, and can be used for large-scale production.
  • the prepared molecular sieve catalyst has a relatively low reaction ratio of benzene to alcohol. High selectivity of ethyl group, low content of xylene impurities, and high hydrothermal stability.
  • the catalyst involved in this application has the characteristics of uniform acid site distribution, high crystallinity, and less waste water produced by the preparation process, which is convenient for scale-up production; the catalyst has good hydrothermal stability in the alkylation reaction between ethanol and benzene, and has lower benzene alcohol. Compared with the feed conditions, it can still maintain high ethyl selectivity, and the xylene impurity content in the product is low, which has a good industrial application prospect.
  • the molecular sieve catalyst described in this application is a small-grain ZSM-5 molecular sieve with high silicon content.
  • the silicon-aluminum molar ratio SiO 2 / Al 2 O 3 of the ZSM-5 molecular sieve is 80 to 140, and the crystal grain diameter of the molecular sieve is 50 to 300 nm.
  • step (1) (2) adding the mixture I containing a silicon source, an aluminum source, an alkali and water to the ZSM-5 seed gel solution described in step (1) to obtain a mixture II, and aging to obtain a solid gel;
  • step (3) Under a sealed condition, the solid gel water-vapor-assisted crystallization described in step (2), roasting I, ammonium ion exchange, roasting II to obtain nano ZSM-5 molecular sieve;
  • step (3) The nano-ZSM-5 molecular sieve obtained in step (3) is subjected to steam treatment and phosphorus modification, and calcined III to obtain the molecular sieve catalyst.
  • the method for obtaining the ZSM-5 seed gel solution in step (1) includes: stirring the solution containing a silicon source and a templating agent, and then refluxing to obtain the ZSM-5 seed gel solution.
  • the molar ratio of the silicon source and the templating agent is 0.5 to 5: 1;
  • the stirring conditions are: stirring at 25-40 ° C in a water bath for 0.5-24 hours;
  • the conditions for the reflux are: in an oil bath at 80 to 160 ° C., the reflux treatment is performed for 24 to 120 hours.
  • the upper limit of the molar ratio of the silicon source and the template is selected from 0.8: 1, 1: 1, 1.2: 1, 1.5: 1, 2: 1, 2.5: 1, 3: 1, 3.5: 1, 4 : 1, 4.5: 1, 4.8: 1 or 5: 1; the lower limit is selected from 0.5: 1, 0.8: 1, 1: 1, 1.2: 1, 1.5: 1, 2: 1, 2.5: 1, 3: 1, 3.5: 1, 4: 1, 4.5: 1 or 4.8: 1.
  • the silicon source is selected from at least one of tetraethyl orthosilicate, silica sol, water glass, and sodium silicate;
  • the template agent is selected from at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium bromide, tetraethylammonium hydroxide, and tetrapropylammonium chloride.
  • the molar ratio of silicon source, aluminum source, alkali and water in the mixture I in step (2) satisfies:
  • SiO 2 : Al 2 O 3 : M 2 O: H 2 O 10 ⁇ 300: 1: 0.1 ⁇ 20: 10 ⁇ 200;
  • water is calculated in the number of moles of H 2 O itself
  • silicon source is calculated in the number of moles of SiO 2
  • aluminum source is calculated in the number of moles of Al 2 O 3
  • alkali is calculated in the number of moles of alkali metal oxide; where M is alkali metal;
  • the ZSM-5 seed gel solution is 5% to 50% of the total mass of the mixture II.
  • the upper limit of the molar ratio (SiO 2 / Al 2 O 3 ) of the silicon source to the aluminum source in the mixture I is selected from 20, 30, 40, 50, 60, 80, 100, 120, 150, 180, 200 , 230, 250, 280, or 300; the lower limit is selected from 10, 20, 30, 40, 50, 60, 80, 100, 120, 150, 180, 200, 230, 250, or 280.
  • the upper limit of the molar ratio (M 2 O / Al 2 O 3 ) of the base to the aluminum source in the mixture I is selected from 0.2, 0.5, 0.8, 1.0, 1.5, 1.8, 2.0, 2.5, 3, 5 , 8 , 10, 12, 15, 18, or 20; the lower limit is selected from 0.1, 0.2, 0.5, 0.8, 1.0, 1.5, 1.8, 2.0, 2.5, 3, 5, 8, 10, 12, 15, or 18.
  • the upper limit of the molar ratio (H 2 O / Al 2 O 3 ) of water to the aluminum source in the mixture I is selected from 15, 20, 30, 50, 60, 80, 100, 120, 150, 180, or 200 ;
  • the lower limit is selected from 10, 15, 20, 30, 50, 60, 80, 100, 120, 150, or 180.
  • the upper limit of the proportion of the ZSM-5 seed gel solution to the total mass of the mixture II is selected from 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45 % Or 50%; the lower limit is selected from 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%.
  • the silicon source in step (2) is selected from at least one of tetraethyl orthosilicate, silica sol, water glass, and sodium silicate. That is, the silicon source is any one or more mixed silicon sources of tetraethyl orthosilicate, silica sol, water glass, and sodium silicate.
  • the aluminum source is selected from at least one of sodium metaaluminate, aluminum powder, aluminum nitrate, and aluminum hydroxide. That is, the aluminum source is any one or more mixed aluminum sources of sodium metaaluminate, aluminum powder, aluminum nitrate, and aluminum hydroxide.
  • the base is selected from at least one of sodium hydroxide and potassium hydroxide. That is, the base is one or a mixture of sodium hydroxide and potassium hydroxide.
  • the aging conditions described in step (2) are: stirring at room temperature for 6 to 36 hours, and then stirring in a water bath at 40 to 70 ° C.
  • the aging conditions described in step (2) are: stirring at room temperature for 12 to 36 hours, and then stirring in a water bath at 40 to 70 ° C.
  • the conditions for the steam-assisted crystallization described in step (3) are: crystallization at 120 to 180 ° C. for 10 to 60 hours.
  • the upper limit of the crystallization temperature is selected from 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C, or 180 ° C; and the lower limit is selected from 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C, or 170 ° C. °C.
  • the upper limit of the crystallization time is selected from 15h, 18h, 20h, 24h, 25h, 30h, 35h, 38h, 40h, 45h, 48h, 50h, 55h or 60h; the lower limit is selected from 10h, 15h, 18h, 20h, 24h, 25h, 30h, 35h, 38h, 40h, 45h, 48h, 50h or 55h.
  • the conditions for firing I in step (3) are: firing at 300 to 600 ° C for 1 to 10 hours;
  • roasting II The conditions for the roasting II are: roasting at 400 to 600 ° C for 1 to 3 hours.
  • the conditions for the roasting II are: roasting at 500 ° C for 2h.
  • the upper limit of the temperature of the roasting I is 350 ° C, 400 ° C, 450 ° C, 500 ° C, 550 ° C, or 600 ° C; the lower limit is selected from 300 ° C, 350 ° C, 400 ° C, 450 ° C, 500 ° C, or 550 ° C .
  • the upper temperature limit of the roasting I is 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10h; the lower limit is selected from 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, or 9h .
  • the heating rate of the roasting I is 8 to 12 ° C / min.
  • the heating rate of the roasting I is 10 ° C / min.
  • the conditions for the steam treatment in step (4) are: the pressure is normal pressure, the temperature is 300-700 ° C, and the time is 0.5-10 hours.
  • the upper limit of the temperature of the water vapor treatment is selected from 350 ° C, 400 ° C, 450 ° C, 500 ° C, 550 ° C, 600 ° C, 650 ° C, or 700 ° C; the lower limit is selected from 300 ° C, 350 ° C, 400 ° C, 450 ° C, 500 ° C, 550 ° C, 600 ° C or 650 ° C.
  • the upper limit of the water vapor treatment time is selected from 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h , 8.5h, 9h, 9.5h or 10h.
  • the water vapor treatment includes: passing nitrogen through a water holding device and carrying water vapor through a molecular sieve bed, wherein a flow rate of the nitrogen is 2 to 50 ml / min.
  • the method used for the water vapor treatment is that nitrogen gas passes through the water holding device and carries water vapor through the molecular sieve bed, wherein the flow rate of the nitrogen gas is 2 to 50 ml / min.
  • the conditions for the phosphorus modification in step (4) are: placing the sample to be treated in a phosphorus-containing solution, and stirring;
  • the mass ratio of the phosphorus-containing solution to the sample to be processed is 1-50.
  • the weight ratio of the phosphorus-containing solution and the ZSM-5 molecular sieve is 1-50.
  • the upper limit of the mass ratio of the phosphorus-containing solution to the sample to be processed is selected from 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, or 50; the lower limit is selected from 1, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, or 45.
  • the concentration of the phosphorus-containing solution is 0.02 to 10 mol / L;
  • the stirring conditions are: stirring in a water bath at 20 to 90 ° C for 0.5 to 15 hours, and the stirring speed is 50 to 400 rpm.
  • the upper limit of the concentration of the phosphorus-containing solution is selected from 0.1 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L L, 4mol / L, 4.5mol / L, 5mol / L, 5.5mol / L, 6mol / L, 6.5mol / L, 7mol / L, 7.5mol / L, 8mol / L, 8.5mol / L, 9mol / L , 9.5mol / L or 10mol / L; the lower limit is selected from 0.05mol / L, 0.1mol / L, 0.5mol / L, 1mol / L, 1.5mol / L, 2mol / L, 2.5mol / L, 3mol / L, 3.5mol / L, 4mol / L, 4.5mol / L, 5mol / L, 5.5mol / L, 5.5
  • the phosphorus source of the phosphorus-containing solution includes at least one of phosphoric acid, diammonium phosphate, diammonium hydrogen phosphate, and ammonium phosphate;
  • the concentration of the phosphorus-containing solution is 0.1 to 5 mol / L.
  • the concentration of the phosphoric acid is 85% by weight.
  • the conditions for roasting III in step (4) are: roasting at 200 to 700 ° C for 1 to 10 hours.
  • the upper temperature limit of the roasting III is selected from 250 ° C, 300 ° C, 350 ° C, 400 ° C, 450 ° C, 500 ° C, 550 ° C, 600 ° C, 650 ° C, or 700 ° C; and the lower limit is selected from 200 ° C, 250 ° C, 300 ° C, 350 ° C, 400 ° C, 450 ° C, 500 ° C, 550 ° C, 600 ° C or 650 ° C.
  • the upper time limit of the roasting III is selected from 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h , 9h, 9.5h or 10h.
  • the molecular sieve catalyst is a small-grain ZSM-5 molecular sieve with a high silicon content.
  • the molecular sieve catalyst is a small-grain ZSM-5 molecular sieve with a grain diameter of 20 to 500 nm;
  • the molecular sieve catalyst has a crystal grain diameter of 50-300 nm.
  • the molecular sieve catalyst has a silicon-aluminum molar ratio SiO 2 / Al 2 O 3 of 50-200.
  • the molecular sieve catalyst has a silicon-aluminum molar ratio SiO 2 / Al 2 O 3 of 80-140.
  • the upper limit of the silicon-aluminum molar ratio SiO 2 / Al 2 O 3 of the molecular sieve catalyst is selected from 60, 70, 80, 82, 84, 90, 92, 96, 100, 107, 110, 112, 113, 120 , 124, 130, 132, 136, 140, 150, 160, 170, 180, 190 or 200.
  • the method for preparing the molecular sieve catalyst includes:
  • the silicon source was weighed and dissolved in deionized water, and a template agent was added, and the mixture was stirred in a water bath at 25 to 40 ° C for 0.5 to 24 hours; then transferred to an oil bath at 80 to 160 ° C and subjected to reflux treatment for 24 to 120 hours to obtain a seed gel solution. ;
  • the silicon source, aluminum source, alkali, and water were weighed according to the ratio and stirred to obtain a mixture.
  • the molar ratios of the materials in the mixture were SiO 2 , Al 2 O 3 , M 2 O, and H 2 O, respectively.
  • SiO 2 : Al 2 O 3 : M 2 O: H 2 O 10 ⁇ 300: 1: 0.1 ⁇ 20: 10 ⁇ 200, where M is an alkali metal; add the above mixture to the seed gel solution, and stir at room temperature for 12 ⁇ 36h , Placed in a water bath at 40 to 70 ° C and stirred to evaporate water in the solution to obtain a solid gel;
  • water is calculated in the number of moles of H 2 O itself
  • silicon source is calculated in the number of moles of SiO 2
  • aluminum source is calculated in the number of moles of Al 2 O 3
  • alkali is calculated in the number of moles of alkali metal oxide; where M is alkali metal;
  • the solid gel is ground into a powder and placed on a bracket; the whole is placed in a hydrothermal kettle containing 1-10 ml of water and sealed; placed at 120-180 ° C for crystallization and kept at a constant temperature for 10-60 hours; The product was filtered and washed until the washing solution became neutral, filtered, and dried at 60 to 120 ° C; then the sample was baked at 300 to 600 ° C for 1 to 10 hours; then, ammonium exchange and roasted to obtain ZSM-5 molecular sieve;
  • the conditions for the ammonium ion exchange are: 3 times exchange with a 1 mol / L ammonium nitrate solution in a 70 ° C water bath condition;
  • the sample obtained in 3) is subjected to steam treatment, wherein the processing conditions are normal pressure, the temperature is 300-700 ° C, and the time is 0.5-10 hours; the treated sample is placed in a phosphorus-containing solution in a water bath, and the phosphorus-containing solution is stirred.
  • the concentration is 0.02 to 10 mol / L, the water bath temperature is 20 to 90 ° C, the stirring speed is 50 to 400 rpm, and the time is 0.5 to 15 hours; the treated sample is filtered and washed until the washing solution becomes neutral, and filtered, Drying treatment is performed at 60 to 120 ° C; the sample is then baked at 200 to 700 ° C for 1 to 10 hours to obtain the molecular sieve catalyst.
  • the method for preparing the molecular sieve catalyst includes:
  • the silicon source was weighed and dissolved in deionized water, and a template agent was added, and the mixture was stirred in a water bath at 25 to 40 ° C for 0.5 to 24 hours; then transferred to an oil bath at 80 to 160 ° C and subjected to reflux treatment for 24 to 120 hours to obtain a seed gel solution. .
  • the solid gel is ground into a powder and placed on a polytetrafluoroethylene bracket; the whole is placed in a hydrothermal kettle containing 1-10 ml of water and sealed; placed in an oven at 120-180 ° C for crystallization and kept at a constant temperature 10 ⁇ 60h; filtering and washing the obtained product until the washing liquid becomes neutral, and the filtered cake is transferred to an oven at 60 ⁇ 120 °C for drying treatment; then the sample is roasted in a muffle furnace at 300 ⁇ 600 °C 1 ⁇ 10h; the catalyst is exchanged 3 times with ammonium nitrate solution (1mol / L, 70 ° C water bath), and calcined to obtain ZSM-5 molecular sieve.
  • the sample obtained in step 3 is placed in a tube furnace for water vapor treatment, where the treatment conditions are normal pressure, the temperature is 300-700 ° C, and the time is 0.5-10 hours. Place the treated sample in a flask, add a phosphorus-containing solution, and transfer to a water bath for further processing.
  • the concentration of the phosphorus-containing solution is 0.02 to 10 mol / L
  • the water bath temperature is 20 to 90 ° C
  • the stirring speed is 50 to 400 rpm. Minutes and time is 0.5 ⁇ 15h.
  • the processed sample is filtered and washed until the washing liquid becomes neutral, and the filtered cake is transferred to an oven at 60-120 ° C for drying treatment; then the sample is baked in a 200-700 ° C muffle furnace for 1-10 hours That is, a catalyst for gas-phase alkylation of ethanol and benzene to prepare ethylbenzene is obtained.
  • the silicon source is any one or more mixed silicon sources of tetraethyl orthosilicate, silica sol, water glass, and sodium silicate; template agents are tetrapropylammonium hydroxide and tetrapropylammonium bromide. Or any mixture of tetraethylammonium bromide, tetraethylammonium hydroxide, and tetrapropylammonium chloride.
  • the silicon source in step 2 is any one or more mixed silicon sources of tetraethyl orthosilicate, silica sol, water glass, and sodium silicate;
  • the aluminum source is sodium metaaluminate, aluminum powder, aluminum nitrate, and hydrogen Any one or more mixed aluminum sources in alumina;
  • the base is any one or two mixtures of sodium hydroxide and potassium hydroxide.
  • the weight ratio of the seed gel solution added in step 2 to the mixture is 5% to 50%.
  • the method used for the high-temperature water vapor treatment in step 4 is that nitrogen passes through the H 2 O-containing device and carries water vapor through the molecular sieve bed.
  • the flow rate of nitrogen is 2-50 ml / min.
  • the phosphorus source used in step 4 is any one or two mixed phosphorous sources of 85% strength phosphoric acid, monoammonium phosphate, diammonium hydrogen phosphate, and ammonium phosphate; the concentration of the phosphorus-containing solution used is 0.1 to 5 mol / L. ; The weight ratio of the phosphorus-containing solution and the ZSM-5 molecular sieve is 1 to 50.
  • a catalyst for preparing ethylbenzene by gas-phase alkylation of ethanol and benzene comprises at least one of a molecular sieve catalyst prepared according to any one of the methods described above.
  • a method for preparing ethylbenzene by gas-phase alkylation of ethanol and benzene comprises: passing a raw material containing ethanol and benzene through a fixed-bed reactor containing a catalyst and reacting to obtain ethyl benzene;
  • the catalyst is selected from at least one of molecular sieve catalysts prepared according to any one of the methods described above.
  • the conditions for the reaction are:
  • the molar ratio of benzene to ethanol is 4 to 6: 1; the mass space velocity of ethanol is 0.5 to 2.5 h -1 , the reaction pressure is 0.5 to 2.5 MPa, and the reaction temperature is 300 to 500 ° C.
  • the upper limit of the molar ratio of benzene to ethanol is selected from 4.5: 1, 4.8: 1, 5: 1, 5.2: 1, 5.5: 1, 5.8: 1, or 6: 1; and the lower limit is selected from 4: 1. 4.5: 1, 4.8: 1, 5: 1, 5.2: 1, 5.5: 1, or 5.8: 1.
  • the upper limit of the mass space velocity of the ethanol is selected from 0.8h -1 , 1.0h -1 , 1.2h -1 , 1.5h -1 , 1.8h -1 , 2.0h -1 or 2.5h -1 ; It is selected from 0.5h -1 , 0.8h -1 , 1.0h -1 , 1.2h -1 , 1.5h -1 , 1.8h -1 or 2.0h -1 .
  • the upper limit of the reaction pressure is selected from 0.8 MPa, 1.0 MPa, 1.2 MPa, 1.5 MPa, 1.8 MPa, 2.0 MPa, or 2.5 MPa; the lower limit is selected from 0.5 MPa, 0.8 MPa, 1.0 MPa, 1.2 MPa, 1.5 MPa, 1.8MPa or 2.0MPa.
  • the upper limit of the reaction temperature is selected from 320 ° C, 350 ° C, 380 ° C, 400 ° C, 450 ° C, 480 ° C, or 500 ° C; the lower limit is selected from 300 ° C, 320 ° C, 350 ° C, 380 ° C, 400 ° C, 450 ° C or 480 ° C.
  • the present application adopts a method of combining seed crystals with a solid phase crystallization method in a gel solution to synthesize nano-ZSM-5 molecular sieves with high crystallinity, which are used for gas-phase alkylation of ethanol and benzene after water vapor treatment and phosphorus modification.
  • Preparation of ethylbenzene Under relatively low benzyl alcohol (4-6: 1) process conditions, the catalyst not only has high ethyl selectivity, low xylene content in the product, but also has high resistance to hydrothermal stability.
  • the catalyst prepared by the present application can generate ethylbenzene with high selectivity under relatively low phenol ratio, and the xylene impurity content in the product is low, which saves energy consumption and reduces production cost for subsequent product separation.
  • the catalyst prepared by this application has strong stability, long regeneration period, saves investment cost, and has high applicable value.
  • FIG. 1 is an XRD pattern of the ZSM-5 catalyst in Example 1 before treatment.
  • FIG. 2 is an XRD pattern of the ZSM-5 catalyst treated in Example 1.
  • FIG. 3a is a SEM image of the ZSM-5 catalyst in Example 1 before treatment
  • FIG. 3b is a SEM image of the ZSM-5 catalyst in Example 1 after water vapor and phosphoric acid treatment.
  • FIG. 4 is a schematic diagram of the ethanol conversion rate of the catalyst used in the ethanol to ethylbenzene reaction in Example 1.
  • FIG. 4 is a schematic diagram of the ethanol conversion rate of the catalyst used in the ethanol to ethylbenzene reaction in Example 1.
  • FIG. 5 is a schematic diagram of ethylbenzene selection performance of the catalyst used in the ethanol production reaction of ethylbenzene in Example 1.
  • FIG. 5 is a schematic diagram of ethylbenzene selection performance of the catalyst used in the ethanol production reaction of ethylbenzene in Example 1.
  • FIG. 6 is a schematic diagram of the content of xylene relative to ethylbenzene in the reaction product of the catalyst used for ethanol to ethylbenzene in Example 1.
  • FIG. 6 is a schematic diagram of the content of xylene relative to ethylbenzene in the reaction product of the catalyst used for ethanol to ethylbenzene in Example 1.
  • the solvent of the solution used in the examples is water.
  • the PANAlytical Epsilon 5 energy dispersive X-ray fluorescence spectrometer XRF was used for the silicon-aluminum ratio test.
  • Micromeritics ASAP-2010 type physical adsorption instrument was used for pore structure test.
  • the ethanol conversion rate, ethyl selectivity, and relative xylene content are all calculated based on the number of moles of carbon:
  • Ethanol conversion rate (moles of ethanol feed-moles of ethanol in the product) / moles of ethanol feed
  • Ethyl selectivity (moles of ethylbenzene in the product + moles of diethylbenzene in the product ⁇ 2) / moles of ethanol feed
  • Relative xylene content moles of xylene in the product / moles of ethylbenzene in the product
  • the ZSM-5 molecular sieve is placed in a reaction tube and treated with water vapor at 500 ° C. for 2 hours at normal pressure; a 1 mol / L phosphoric acid solution is weighed and the treated sample is mixed at a weight ratio of 5: 1 and placed at 50 ° Stir in a water bath for 2h (300 rpm), then filter and wash until the washing solution becomes neutral, dry the collected solid precipitate at 110 ° C for 12h, and calcine at 550 ° C for 4h to obtain the catalyst, labeled as 1 #.
  • the XRD patterns of the prepared catalysts before and after treatment, and the SEM images before and after treatment are shown in Figures 1 to 3, respectively.
  • the molecular sieve can still maintain its MFI topology structure after hydrothermal and phosphoric acid modification treatment, and the morphology of the molecular sieve does not change much, which indicates that the synthesized molecular sieve has good resistance to hydrothermal stability.
  • Example 1 The ethyl orthosilicate in step 1) of Example 1 was replaced with 24.0 g of a silica sol (30 wt%) with an equimolar silicon content, and the remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was marked as 2 #.
  • Example 1 The tetrapropylammonium hydroxide solution in step 1) of Example 1 was replaced with 6.3 g of tetraethylammonium bromide in an equimolar amount, and the remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was marked as 3 #.
  • Example 2 20.0 g of tetraethyl silicate and 0.3 g of sodium hydroxide in step 2) of Example 1 were replaced with 18.0 g of water glass and 0.42 g of potassium hydroxide, and the rest of the synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, labeled 5 #.
  • Example 2 The 8g ZSM-5 seed solution in step 2) of Example 1 was replaced with 15g ZSM-5 seed solution, and the remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was marked as 6 #.
  • Example 2 The 0.7 g of sodium metaaluminate and 8 g of ZSM-5 seed solution in step 2) of Example 1 were replaced with 0.9 g of aluminum nitrate nonahydrate and 12 g of ZSM-5 seed solution, and the remaining synthesis conditions remained unchanged to obtain a molecular sieve. Catalyst, labeled 7 #.
  • the ZSM-5 molecular sieve is placed in a reaction tube and treated with water vapor at 500 ° C. for 2 hours at normal pressure; a 1 mol / L phosphoric acid solution is weighed and the treated sample is mixed at a weight ratio of 5: 1 and placed at 50 ° C. Stir in a water bath for 2h (300 rpm), then filter and wash until the washing solution becomes neutral, dry the collected solid precipitate at 110 ° C for 12h, and calcine at 550 ° C for 4h to obtain the used catalyst, labeled 9 # .
  • Example 1 The processing time of the water vapor in step 4) of Example 1 was changed from 2h to 4h at 500 ° C under normal pressure, and the remaining synthesis conditions were kept unchanged to obtain a molecular sieve catalyst, labeled 10 #.
  • Example 1 The phosphorus treatment conditions in step 4) of Example 1 were mixed from a 1 mol / L phosphoric acid solution with the treated sample at a weight ratio of 5: 1 and replaced with a 4 mol / L diammonium hydrogen phosphate solution and the treated sample with The weight ratio of 2: 1 was mixed, and the remaining synthesis conditions were kept unchanged to obtain a molecular sieve catalyst, which was labeled 11 #.
  • Example 1 The phosphorus treatment conditions in step 4) of Example 1 were mixed from a 1 mol / L phosphoric acid solution and the treated sample at a weight ratio of 5: 1 and replaced with a 0.2 mol / L ammonium dihydrogen phosphate solution and the treated sample. The mixture was mixed at a weight ratio of 30: 1, and the remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was marked as 12 #.
  • step 2) in Example 1 was replaced with 36h, and the temperature of the water bath was replaced with 40 ° C; the remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was labeled 15 #.
  • step 2) in Example 1 was replaced with 12h, and the temperature of the water bath was replaced with 70 ° C; the remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was labeled 16 #.
  • Example 3 Replace the crystallization temperature in step 3) in Example 1 with 120 ° C and the crystallization time with 60h; the roasting temperature before the ammonium nitrate solution exchange is replaced with 300 ° C, the roasting time is 10h, and the heating rate is replaced with 8 ° C / min, the remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, labeled 17 #.
  • Example 3 Replace the crystallization temperature in step 3) in Example 1 with 180 ° C and the crystallization time with 10h; the roasting temperature before the ammonium nitrate solution exchange is replaced with 600 ° C, the roasting time is 1h, and the heating rate is replaced with 12 ° C / min, the remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, labeled 18 #.
  • Example 2 The calcination temperature after the exchange of the ammonium nitrate solution in step 3) in Example 1 was replaced with 600 ° C., and the calcination time was 1 h. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was marked as 19 #.
  • Example 2 The calcination temperature after the exchange of the ammonium nitrate solution in step 3) in Example 1 was replaced with 400 ° C., and the calcination time was 3 hours. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was marked as 20 #.
  • Example 1 The temperature of the steam treatment in step 4) in Example 1 was replaced by 300 ° C., and the treatment time was replaced by 10 h. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was labeled 21 #.
  • Example 1 The temperature of the steam treatment in step 4) in Example 1 was replaced with 700 ° C., and the treatment time was replaced with 0.5 h. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was labeled 22 #.
  • Example 1 The concentration of the phosphoric acid solution in step 4) in Example 1 was replaced by 0.02 mol / L, and the weight ratio of the phosphoric acid solution to the treated sample was replaced by 50: 1. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained. For 23 #.
  • Example 1 The concentration of the phosphoric acid solution in step 4) in Example 1 was replaced by 10 mol / L, and the weight ratio of the phosphoric acid solution to the treated sample was replaced by 1: 1. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, labeled as twenty four#.
  • Example 1 The temperature of the water bath stirring in step 4) in Example 1 was replaced with 20 ° C., and the stirring time was replaced with 15 h. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was marked as 25 #.
  • Example 1 The temperature of the water bath stirring in step 4) in Example 1 was replaced by 90 ° C., and the stirring time was replaced by 0.5 h. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was marked as 26 #.
  • Example 1 The calcination temperature in step 4) in Example 1 was replaced with 200 ° C, and the calcination time was replaced with 10 hours. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was labeled 27 #.
  • Example 1 The calcination temperature in step 4) in Example 1 was replaced by 90 ° C., and the calcination time was replaced by 1 h. The remaining synthesis conditions were kept unchanged, and a molecular sieve catalyst was obtained, which was labeled 28 #.
  • Example 1 The molar ratios of ethyl orthosilicate and tetrapropylammonium hydroxide in step 1) in Example 1 were replaced by 0.5: 1, 2.5: 1, and 5: 1, respectively; the rest of the operations and conditions were the same as in Example 1 to obtain Molecular sieve catalysts are labeled 29 #, 30 # and 31 # respectively.
  • Example 1 The stirring rate in the water bath in step 4) in Example 1 was replaced by 400 rpm and 50 rpm, respectively; the rest of the operations and conditions were the same as in Example 1 to obtain a molecular sieve catalyst, labeled 32 # and 33, respectively. #.
  • the relative crystallinity of the sample is based on Example 1 and is defined as 100%.
  • Example 13 to 16 The test results of Examples 13 to 16 are similar to the above, the particle size range is 20-500 nm, and the SiO 2 / Al 2 O 3 molar ratio is 50-200.
  • the catalyst (50g) in each of the above embodiments was charged into a reaction tube of a fixed-bed reaction bed for reaction evaluation.
  • the raw materials were benzene and ethanol, and the molar ratio of benzene to ethanol was 4: 1; the reaction temperature was 400 ° C and the mass of ethanol The space velocity is 1.2h -1 and the reaction pressure is 1.5MPa.
  • the reaction products were analyzed by online gas chromatography.
  • the ethanol conversion rate, ethylbenzene selectivity, and xylene content in the product obtained by using the sample of Example 1 as a catalyst are sequentially shown in FIGS. 4 to 6.
  • the reaction results of the above catalysts are shown in Table 2 under the same reaction conditions. It can be seen from the figure that the long-term reaction performance of the reaction is stable, the ethanol conversion rate is> 99%, the ethyl selectivity is> 99%, and the xylene impurity content in the stabilized product is less than 800 ppm.
  • the catalyst was prepared by referring to the catalyst preparation method of Example 1 disclosed in the patent CN102372580B and used in the experimental reaction conditions in Example 18. The results of the catalytic reaction are shown in Table 2.
  • the modified catalyst was used in the reaction conditions in Example 18.
  • the catalytic reaction results are shown in Table 2.
  • the experimental reaction conditions and catalytic reaction results are shown in Table 2.
  • Table 2 shows the catalyst performance test structures of Examples 1 to 12, Comparative Example 1, and Comparative Example 2.
  • the catalyst (50g) in each of the above embodiments was charged into a reaction tube of a fixed-bed reaction bed for reaction evaluation.
  • the raw materials were benzene and ethanol, and the molar ratio of benzene to ethanol was 6: 1; the reaction temperature was 450 ° C and the mass of ethanol The space velocity is 0.8h -1 and the reaction pressure is 1.5MPa.
  • the reaction products were analyzed by online gas chromatography. The results of the catalytic reactions of the examples are shown in Table 3.
  • the catalyst was prepared by referring to the catalyst preparation method of Example 1 disclosed in the patent CN102372580B and used for the reaction conditions in Example 19. The results of the catalytic reaction are shown in Table 3.
  • the modified catalyst was used in the reaction conditions in Example 19, and the catalytic reaction results are shown in Table 3.
  • the experimental reaction conditions and catalytic reaction results are shown in Table 3.
  • Example 1 The sample (50 g) in Example 1 was packed in a reaction tube of a fixed-bed reaction bed for reaction evaluation.
  • the raw materials were benzene and ethanol, and the molar ratio of benzene to ethanol was 5: 1; the reaction temperature was 300 ° C, and the ethanol mass was empty.
  • the speed is 2.5h -1 and the reaction pressure is 0.5MPa.
  • the reaction products were analyzed by online gas chromatography. The catalytic effect is similar to the test results of Example 1 in Table 1.
  • Example 1 The sample (50 g) in Example 1 was charged into a reaction tube of a fixed-bed reactor for reaction evaluation.
  • the raw materials were benzene and ethanol, and the molar ratio of benzene to ethanol was 4: 1; the reaction temperature was 300 ° C, and the ethanol mass was empty.
  • the speed is 2.5h -1 and the reaction pressure is 0.5MPa.
  • the reaction products were analyzed by online gas chromatography. The catalytic effect is similar to the test results of Example 1 in Table 1.
  • phase structure analysis is performed on the molecular sieves obtained in Examples 1 to 16 without water vapor treatment and phosphorus modification, and the corresponding molecular sieve catalysts. Typical examples are shown in FIGS. 1 to 2.
  • FIG. 1 is an XRD pattern of the molecular sieve without water vapor treatment and phosphorus modification in Example 1
  • FIG. 2 is an XRD pattern of the sample 1 # in Example 1. It can be seen from the figure that the synthesized parent molecular sieve is relatively crystallized It has a high degree. Although the relative crystallinity is significantly reduced after steam treatment and phosphorylation modification, it can still maintain the MFI topology.
  • Fig. 3a corresponds to the electron microscope photograph of the molecular sieve obtained in Example 1 without post-treatment
  • Fig. 3b corresponds to the electron microscope photograph of the molecular sieve obtained in Example 1 after water vapor and phosphoric acid modification treatment
  • the particle distribution is more uniform.

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Abstract

L'invention concerne un procédé de préparation d'un catalyseur à tamis moléculaire. Le procédé comprend les étapes consistant à : obtenir une solution de gel de germe cristallin de ZSM-5; ajouter un mélange I contenant une source de silicium, une source d'aluminium, un alcali et de l'eau à la solution de gel de germe cristallin de ZSM-5 pour obtenir un mélange, et à laisser vieillir celui-ci pour obtenir un gel solide; dans une condition scellée, soumettre le gel solide à une cristallisation assistée à la vapeur d'eau, calciner celui-ci, réaliser un échange d'ions ammonium, et calciner celui-ci pour obtenir un tamis moléculaire ZSM -5 de taille nanométrique; et soumettre le tamis moléculaire ZSM -5 de taille nanométrique obtenu à un traitement à la vapeur d'eau et à une modification du phosphore, et calciner celui-ci pour obtenir le catalyseur à tamis moléculaire. Le catalyseur présente les caractéristiques d'une distribution uniforme de sites acides et d'une cristallinité élevée, et le processus de préparation de celui-ci produit moins d'eaux usées, ce qui est pratique pour une production à l'échelle. Le catalyseur a une bonne stabilité hydrothermique pendant une réaction d'alkylation entre l'éthanol et le benzène, peut maintenir une sélectivité élevée à l'éthyle dans la condition d'un rapport benzène-éthanol inférieur; en outre, il y a une faible teneur en impuretés de xylène dans le produit. Il en est de même de bonnes perspectives d'application industrielles.
PCT/CN2018/106165 2018-09-07 2018-09-18 Procédé de préparation et utilisation de catalyseur à tamis moléculaire WO2020047902A1 (fr)

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