CN108722406B - Tungsten-based catalyst, preparation method and application thereof in isobutane-butylene alkylation reaction - Google Patents

Tungsten-based catalyst, preparation method and application thereof in isobutane-butylene alkylation reaction Download PDF

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CN108722406B
CN108722406B CN201810560960.1A CN201810560960A CN108722406B CN 108722406 B CN108722406 B CN 108722406B CN 201810560960 A CN201810560960 A CN 201810560960A CN 108722406 B CN108722406 B CN 108722406B
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赵洪起
燕东雁
张海鹏
王文亮
侯永海
胡宗泉
张斌
丛广海
王鹏
武海峰
陈鑫诚
吕小丽
门学磊
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Abstract

The invention relates to a tungsten-based catalyst, a preparation method and application thereof in isobutane-butylene alkylation reaction, belonging to the technical field of fine chemical engineering. The invention provides W/Ir @ Al2O3The catalyst takes Mn-doped hollow porous alumina microspheres as a carrier, and W and Ir are loaded on the carrier, so that the catalyst has higher reaction activity and selectivity in the isobutane-butylene alkylation reaction and the service life of the catalyst.

Description

Tungsten-based catalyst, preparation method and application thereof in isobutane-butylene alkylation reaction
Technical Field
The invention relates to a tungsten-based catalyst, a preparation method and application thereof in isobutane-butylene alkylation reaction, belonging to the technical field of fine chemical engineering.
Background
Another important means for improving the quality of gasoline is to improve the components of gasoline itself and try to increase the high-octane component oils in the gasoline components, such as alkylate, isomerate, gasoline, etc. Isobutane and butene can produce high octane gasoline under acid catalysis, and the C4 alkylation reaction is one of the important refinery processes. The alkylated gasoline has low Reynolds steam pressure and contains no arene and olefin basically, so that it is ideal fuel oil for vehicle. Concentrated sulfuric acid and hydrofluoric acid are commonly used in industrial alkylation reaction, but the two liquid acids have the disadvantages of high corrosion and strong pollution, so that the research and development of a new, safe and friendly catalyst is the research trend of C4 alkylation reaction. The alkylation reaction mechanism research is reported in the literature mostly, follows the carbonium ion reaction mechanism and is a B acid catalytic system. The reaction intermediate is carbonium ion, which is different from liquid acid catalytic system, and the reaction intermediate of solid acid catalytic system is adsorption state carbonium ion.
The traditional alkylated gasoline production process uses liquid acid catalyst, such as hydrofluoric acid, sulfuric acid and the like, but the liquid acid catalyst has the problems of high acid consumption, equipment corrosion, difficult treatment of waste sulfuric acid, HF corrosive volatilization and other environmental pollution and safety problems. Therefore, the development of solid acid catalysts which can meet the requirements of safety and environmental protection and are easy to regenerate and the production process are focused at home and abroad. At present, the solid acid catalysts which are researched mainly comprise molecular sieves, heteropoly acids, solid superacids and the like, and the problems of rapid inactivation and poor selectivity exist, so that industrialization is difficult to realize.
Disclosure of Invention
The purpose of the invention is: aiming at the alkylation reaction of isobutane and butene, a solid acid catalyst is provided, porous hollow microspheres are used as a carrier, and a W/Ir active center is loaded on the surface of the carrier. The catalyst has high reaction activity and selectivity.
The technical scheme is as follows:
a preparation method of a tungsten-based catalyst comprises the following steps:
step 1, preparing monodisperse polystyrene-methacrylic acid composite microspheres: mixing 5-8 parts by weight of styrene, 1-1.5 parts by weight of divinylbenzene and 0.3-0.6 part by weight of methacrylic acid, adding 0.3-0.5 part by weight of dibenzoyl peroxide as an initiator, uniformly stirring, adding the mixture into 8-12 parts by weight of aqueous solution of polyvinyl alcohol with the concentration of 2-4 wt%, dispersing at a high speed, heating to perform a first reaction, adding sodium dodecyl benzene sulfonate into the reaction solution to enable the concentration of the sodium dodecyl benzene sulfonate in the reaction solution to be 0.3-0.5 wt%, heating to perform a second reaction, centrifugally separating a polymerization product, washing with deionized water, and drying in vacuum to obtain monodisperse polystyrene-methacrylic acid composite microspheres;
step 2, the surface of the microsphere is subjected to charge treatment: dispersing 2-5 parts of monodisperse polystyrene-methacrylic acid composite microspheres in 1-3 wt% of NaOH solution by weight, heating, centrifugally separating the product, washing with deionized water, and drying in vacuum to obtain microspheres with surface charges;
and 3, loading Mn on the surface of the microsphere: dispersing 1-3 parts by weight of surface-charged microspheres and 2-4 parts by weight of manganese sulfate in 300-400 parts by weight of deionized water, keeping the mixture at the temperature of 20-30 ℃ for 12-20 hours, and centrifugally separating the product to obtain Mn loaded on the surface2+The microspheres of (1);
step 4, preparing a hollow porous microsphere carrier: loading Mn on the surface in parts by weight2+Mixing 1-3 parts of microspheres, 30 parts of deionized water and 120-150 parts of ethanolUniformly mixing, adding 2-4 parts of aluminum nitrate and 0.5-0.8 part of urea, adjusting the pH to 7.5-8 by using 5-10 wt% of ammonia water, reacting at 25-35 ℃ for 12-24 h, centrifugally separating precipitates, washing by using deionized water, drying in vacuum, and roasting the product to obtain the hollow porous alumina microsphere carrier;
and 5, preparing Ir nano particle sol: adding H into 0.3-0.6 mol/L dilute hydrochloric acid2IrCl6Let H stand for2IrCl6The concentration of the aqueous solution in dilute hydrochloric acid is 0.8-1.1 wt%, heating for reaction, cooling, adjusting the pH to 6.5-7.5 with NaOH solution, adding Cetyl Trimethyl Ammonium Bromide (CTAB) into the solution to make the concentration of CTAB in the reaction solution be 8-15 mmol/L, and then dropwise adding 40-60 mmol/L NaBH4Carrying out reduction reaction on the solution to obtain Ir nano particle sol;
step 6, loading of active center on the carrier: preparing 1.2-1.8 wt% of H8N2O4Adding Ir nano particle sol into the solution W, and uniformly mixing to obtain a mixed impregnation solution; adding a hollow porous alumina microsphere carrier into the mixed impregnation liquid to enable the concentration of the hollow porous alumina microsphere carrier in the mixed impregnation liquid to be 1-4 wt%, heating to 80-85 ℃, reacting for 2-4 h, drying under reduced pressure, and roasting the solid to obtain W/Ir @ Al2O3A catalyst.
In the step 1, the first reaction is carried out at 75-80 ℃ for 1-1.5 h, and the second reaction is carried out at 90-95 ℃ for 0.5-1 h.
In the step 2, the temperature rise treatment refers to treatment at 40-45 ℃ for 0.5-1.5 h.
In the step 4, roasting is carried out at 650-750 ℃ for 2-4 h.
In the 5 th step, H8N2O4The volume ratio of the W solution to the Ir nanoparticle sol is 3-6: 1, roasting is carried out at 750-800 ℃ for 2-5 h.
A method for preparing isooctane by alkylation of isobutane-butene comprises the following steps:
in the above-mentioned W/Ir @ Al2O3Presence of catalystAnd reacting isobutane and 2-butene in the reactor to obtain isooctane.
The alkane-olefin ratio of isobutane to 2-butene is 7-10: 1, the reaction temperature is 25-40 ℃, and the reaction pressure is 0.40-0.50 MPa.
Advantageous effects
The invention provides W/Ir @ Al2O3The catalyst takes Mn-doped hollow porous alumina microspheres as a carrier, and W and Ir are loaded on the carrier, so that the catalyst has higher reaction activity and selectivity in the isobutane-butylene alkylation reaction and the service life of the catalyst.
Drawings
FIG. 1 is an SEM photograph of hollow porous alumina microspheres prepared according to the present invention.
FIG. 2 is an XRD spectrum of the hollow porous alumina microspheres prepared by the present invention.
FIG. 3 shows W/Ir @ Al prepared according to the present invention2O3XRD pattern of catalyst.
FIG. 4 is a graph showing the change of the cyclic reaction performance of the catalyst provided by the present invention in alkylation reaction.
Detailed Description
EXAMPLE 1 preparation of tungsten-based catalyst
Step 1, preparing monodisperse polystyrene-methacrylic acid composite microspheres: mixing 5 parts of styrene, 1 part of divinylbenzene and 0.3 part of methacrylic acid according to parts by weight, adding 0.3 part of dibenzoyl peroxide as an initiator, uniformly stirring, adding the mixture into 8 parts of a polyvinyl alcohol aqueous solution with the concentration of 2wt%, dispersing at a high speed, reacting at 75 ℃ for 1h, adding sodium dodecyl benzene sulfonate into the reaction solution to ensure that the concentration of the sodium dodecyl benzene sulfonate in the reaction solution is 0.3wt%, reacting at 90 ℃ for 0.5h, centrifugally separating a polymerization product, washing with deionized water, and drying in vacuum to obtain monodisperse polystyrene-methacrylic acid composite microspheres;
step 2, the surface of the microsphere is subjected to charge treatment: dispersing 2 parts of monodisperse polystyrene-methacrylic acid composite microspheres in 1wt% of NaOH solution according to parts by weight, processing for 0.5h at 40 ℃, centrifugally separating products, washing with deionized water, and drying in vacuum to obtain microspheres with surface charges;
and 3, loading Mn on the surface of the microsphere: dispersing 1 part of surface-charged microspheres and 2 parts of manganese sulfate in 300 parts of deionized water by weight, keeping the mixture at 20 ℃ for 12 hours, and centrifugally separating the product to obtain Mn loaded on the surface2+The microspheres of (1);
step 4, preparing a hollow porous microsphere carrier: loading Mn on the surface in parts by weight2+Uniformly mixing 1 part of the microspheres, 30 parts of deionized water and 120 parts of ethanol, adding 2 parts of aluminum nitrate and 0.5 part of urea, adjusting the pH to 7.5-8 by using 5wt% ammonia water, reacting at 25 ℃ for 12 hours, centrifugally separating precipitates, washing by using deionized water, drying in vacuum, and roasting the product at 650 ℃ for 2 hours to obtain a hollow porous alumina microsphere carrier;
and 5, preparing Ir nano particle sol: adding H into 0.3mol/L dilute hydrochloric acid2IrCl6Let H stand for2IrCl6The concentration of the aqueous solution in dilute hydrochloric acid is 0.8wt%, the aqueous solution is heated for reaction, after the temperature is reduced, the pH value is adjusted to 6.5-7.5 by NaOH solution, Cetyl Trimethyl Ammonium Bromide (CTAB) is added into the solution, the concentration of the CTAB in the reaction solution is 8mmol/L, and 40mmol/L NaBH is added dropwise4Carrying out reduction reaction on the solution to obtain Ir nano particle sol;
step 6, loading of active center on the carrier: preparation of 1.2wt% H8N2O4W solution, adding Ir nano particle sol and H8N2O4The volume ratio of the W solution to the Ir nanoparticle sol was 3: 1, uniformly mixing to obtain a mixed impregnation liquid; adding a hollow porous alumina microsphere carrier into the mixed impregnation liquid to ensure that the concentration of the hollow porous alumina microsphere carrier in the mixed impregnation liquid is 1wt%, heating to 80 ℃, reacting for 2h, drying under reduced pressure, and roasting the solid at 750 ℃ for 2h to obtain W/Ir @ Al2O3A catalyst.
EXAMPLE 2 preparation of tungsten-based catalyst
Step 1, preparing monodisperse polystyrene-methacrylic acid composite microspheres: mixing 8 parts of styrene, 1.5 parts of divinylbenzene and 0.6 part of methacrylic acid according to parts by weight, adding 0.5 part of dibenzoyl peroxide as an initiator, uniformly stirring, adding the mixture into 12 parts of a polyvinyl alcohol aqueous solution with the concentration of 4wt%, reacting at 80 ℃ for 1.5h after high-speed dispersion, adding sodium dodecyl benzene sulfonate into a reaction solution to ensure that the concentration of the sodium dodecyl benzene sulfonate in the reaction solution is 0.5wt%, reacting at 95 ℃ for 1h, centrifugally separating a polymerization product, washing with deionized water, and drying in vacuum to obtain the monodisperse polystyrene-methacrylic acid composite microspheres;
step 2, the surface of the microsphere is subjected to charge treatment: dispersing 5 parts of monodisperse polystyrene-methacrylic acid composite microspheres in 3wt% of NaOH solution according to parts by weight, treating for 1.5h at 45 ℃, centrifugally separating products, washing with deionized water, and drying in vacuum to obtain microspheres with surface charges;
and 3, loading Mn on the surface of the microsphere: dispersing 3 parts by weight of surface-charged microspheres and 4 parts by weight of manganese sulfate in 400 parts by weight of deionized water, keeping the mixture at 30 ℃ for 20 hours, and centrifugally separating the product to obtain Mn loaded on the surface2+The microspheres of (1);
step 4, preparing a hollow porous microsphere carrier: loading Mn on the surface in parts by weight2+Uniformly mixing 3 parts of the microspheres, 30 parts of deionized water and 150 parts of ethanol, adding 4 parts of aluminum nitrate and 0.8 part of urea, adjusting the pH to 7.5-8 by using 10wt% ammonia water, reacting at 35 ℃ for 24 hours, centrifugally separating precipitates, washing by using deionized water, drying in vacuum, and roasting the product at 750 ℃ for 4 hours to obtain a hollow porous alumina microsphere carrier;
and 5, preparing Ir nano particle sol: adding H into 0.6mol/L dilute hydrochloric acid2IrCl6Let H stand for2IrCl6The concentration of the aqueous solution in dilute hydrochloric acid is 1.1wt%, the aqueous solution is heated for reaction, after the temperature is reduced, the pH value is adjusted to 6.5-7.5 by NaOH solution, Cetyl Trimethyl Ammonium Bromide (CTAB) is added into the solution, the concentration of the CTAB in the reaction solution is 15mmol/L, and 60mmol/L NaBH is added dropwise4Carrying out reduction reaction on the solution to obtain Ir nano particle sol;
step 6, loading of active center on the carrier: preparation of 1.8wt% H8N2O4W solution, adding Ir nano particle sol and H8N2O4The volume ratio of the W solution to the Ir nanoparticle sol was 6: 1, uniformly mixing to obtain a mixed impregnation liquid; adding a hollow porous alumina microsphere carrier into the mixed impregnation liquid to enable the concentration of the hollow porous alumina microsphere carrier in the mixed impregnation liquid to be wt%, heating to 85 ℃, reacting for 4 hours, drying under reduced pressure, and roasting the solid at 800 ℃ for 5 hours to obtain W/Ir @ Al2O3A catalyst.
EXAMPLE 3 preparation of tungsten-based catalyst
Step 1, preparing monodisperse polystyrene-methacrylic acid composite microspheres: mixing 6 parts of styrene, 1.2 parts of divinylbenzene and 0.5 part of methacrylic acid according to parts by weight, adding 0.4 part of dibenzoyl peroxide as an initiator, uniformly stirring, adding the mixture into 10 parts of polyvinyl alcohol aqueous solution with the concentration of 3wt%, reacting at 77 ℃ for 1.2h after high-speed dispersion, adding sodium dodecyl benzene sulfonate into reaction liquid to ensure that the concentration of the sodium dodecyl benzene sulfonate in the reaction liquid is 0.4wt%, reacting at 92 ℃ for 0.6h, centrifugally separating a polymerization product, washing with deionized water, and drying in vacuum to obtain the monodisperse polystyrene-methacrylic acid composite microspheres;
step 2, the surface of the microsphere is subjected to charge treatment: dispersing 4 parts of monodisperse polystyrene-methacrylic acid composite microspheres in 2wt% of NaOH solution, treating at 42 ℃ for 1.2h, centrifugally separating the product, washing with deionized water, and drying in vacuum to obtain microspheres with surface charges;
and 3, loading Mn on the surface of the microsphere: dispersing 2 parts by weight of surface-charged microspheres and 2-4 parts by weight of manganese sulfate in 350 parts by weight of deionized water, keeping the mixture at 25 ℃ for 15 hours, and centrifugally separating the product to obtain the product with Mn loaded on the surface2+The microspheres of (1);
step 4, preparing a hollow porous microsphere carrier: loading Mn on the surface in parts by weight2+Uniformly mixing 2 parts of the microspheres, 30 parts of deionized water and 130 parts of ethanol, adding 3 parts of aluminum nitrate and 0.6 part of urea, adjusting the pH to 7.5-8 by using 6wt% ammonia water, reacting for 20 hours at 30 ℃, and separatingSeparating the precipitate by a core, washing the precipitate by deionized water, drying the precipitate in vacuum, and roasting the product at 700 ℃ for 3 hours to obtain a hollow porous alumina microsphere carrier;
and 5, preparing Ir nano particle sol: adding H into 0.4mol/L dilute hydrochloric acid2IrCl6Let H stand for2IrCl6The concentration of the aqueous solution in dilute hydrochloric acid is 0.9wt%, the aqueous solution is heated for reaction, after the temperature is reduced, the pH value is adjusted to 6.5-7.5 by NaOH solution, Cetyl Trimethyl Ammonium Bromide (CTAB) is added into the solution, the concentration of the CTAB in the reaction solution is 12mmol/L, and 50mmol/L NaBH is added dropwise4Carrying out reduction reaction on the solution to obtain Ir nano particle sol;
step 6, loading of active center on the carrier: preparation of 1.6wt% H8N2O4W solution, adding Ir nano particle sol and H8N2O4The volume ratio of the W solution to the Ir nanoparticle sol was 4: 1, uniformly mixing to obtain a mixed impregnation liquid; adding a hollow porous alumina microsphere carrier into the mixed impregnation liquid to ensure that the concentration of the hollow porous alumina microsphere carrier in the mixed impregnation liquid is 2wt%, heating to 82 ℃, reacting for 3h, drying under reduced pressure, and roasting the solid at 780 ℃ for 4h to obtain W/Ir @ Al2O3A catalyst.
Comparative example 1
The differences from example 3 are: no Mn is doped in the hollow alumina support.
Step 1, preparing monodisperse polystyrene-methacrylic acid composite microspheres: mixing 6 parts of styrene, 1.2 parts of divinylbenzene and 0.5 part of methacrylic acid according to parts by weight, adding 0.4 part of dibenzoyl peroxide as an initiator, uniformly stirring, adding the mixture into 10 parts of polyvinyl alcohol aqueous solution with the concentration of 3wt%, reacting at 77 ℃ for 1.2h after high-speed dispersion, adding sodium dodecyl benzene sulfonate into reaction liquid to ensure that the concentration of the sodium dodecyl benzene sulfonate in the reaction liquid is 0.4wt%, reacting at 92 ℃ for 0.6h, centrifugally separating a polymerization product, washing with deionized water, and drying in vacuum to obtain the monodisperse polystyrene-methacrylic acid composite microspheres;
step 2, the surface of the microsphere is subjected to charge treatment: dispersing 4 parts of monodisperse polystyrene-methacrylic acid composite microspheres in 2wt% of NaOH solution, treating at 42 ℃ for 1.2h, centrifugally separating the product, washing with deionized water, and drying in vacuum to obtain microspheres with surface charges;
step 3, preparing a hollow porous microsphere carrier: uniformly mixing 2 parts of surface-charged microspheres, 30 parts of deionized water and 130 parts of ethanol in parts by weight, adding 3 parts of aluminum nitrate and 0.6 part of urea, adjusting the pH to 7.5-8 by using 6wt% ammonia water, reacting for 20 hours at 30 ℃, centrifugally separating precipitates, washing by using deionized water, drying in vacuum, and roasting the product for 3 hours at 700 ℃ to obtain a hollow porous alumina microsphere carrier;
and 4, preparing Ir nano particle sol: adding H into 0.4mol/L dilute hydrochloric acid2IrCl6Let H stand for2IrCl6The concentration of the aqueous solution in dilute hydrochloric acid is 0.9wt%, the aqueous solution is heated for reaction, after the temperature is reduced, the pH value is adjusted to 6.5-7.5 by NaOH solution, Cetyl Trimethyl Ammonium Bromide (CTAB) is added into the solution, the concentration of the CTAB in the reaction solution is 12mmol/L, and 50mmol/L NaBH is added dropwise4Carrying out reduction reaction on the solution to obtain Ir nano particle sol;
step 5, loading of active center on the carrier: preparation of 1.6wt% H8N2O4W solution, adding Ir nano particle sol and H8N2O4The volume ratio of the W solution to the Ir nanoparticle sol was 4: 1, uniformly mixing to obtain a mixed impregnation liquid; adding a hollow porous alumina microsphere carrier into the mixed impregnation liquid to ensure that the concentration of the hollow porous alumina microsphere carrier in the mixed impregnation liquid is 2wt%, heating to 82 ℃, reacting for 3h, drying under reduced pressure, and roasting the solid at 780 ℃ for 4h to obtain W/Ir @ Al2O3A catalyst.
Comparative example 2
The differences from example 3 are: the Ir active ingredient is not supported on the surface of the carrier.
Step 1, preparing monodisperse polystyrene-methacrylic acid composite microspheres: mixing 6 parts of styrene, 1.2 parts of divinylbenzene and 0.5 part of methacrylic acid according to parts by weight, adding 0.4 part of dibenzoyl peroxide as an initiator, uniformly stirring, adding the mixture into 10 parts of polyvinyl alcohol aqueous solution with the concentration of 3wt%, reacting at 77 ℃ for 1.2h after high-speed dispersion, adding sodium dodecyl benzene sulfonate into reaction liquid to ensure that the concentration of the sodium dodecyl benzene sulfonate in the reaction liquid is 0.4wt%, reacting at 92 ℃ for 0.6h, centrifugally separating a polymerization product, washing with deionized water, and drying in vacuum to obtain the monodisperse polystyrene-methacrylic acid composite microspheres;
step 2, the surface of the microsphere is subjected to charge treatment: dispersing 4 parts of monodisperse polystyrene-methacrylic acid composite microspheres in 2wt% of NaOH solution, treating at 42 ℃ for 1.2h, centrifugally separating the product, washing with deionized water, and drying in vacuum to obtain microspheres with surface charges;
and 3, loading Mn on the surface of the microsphere: dispersing 2 parts by weight of surface-charged microspheres and 2-4 parts by weight of manganese sulfate in 350 parts by weight of deionized water, keeping the mixture at 25 ℃ for 15 hours, and centrifugally separating the product to obtain the product with Mn loaded on the surface2+The microspheres of (1);
step 4, preparing a hollow porous microsphere carrier: loading Mn on the surface in parts by weight2+Uniformly mixing 2 parts of the microspheres, 30 parts of deionized water and 130 parts of ethanol, adding 3 parts of aluminum nitrate and 0.6 part of urea, adjusting the pH to 7.5-8 by using 6wt% ammonia water, reacting at 30 ℃ for 20 hours, centrifugally separating precipitates, washing by using deionized water, drying in vacuum, and roasting the product at 700 ℃ for 3 hours to obtain a hollow porous alumina microsphere carrier;
step 5, loading of active center on the carrier: preparation of 1.6wt% H8N2O4W solution as impregnation liquid; adding a hollow porous alumina microsphere carrier into the impregnation liquid to ensure that the concentration of the hollow porous alumina microsphere carrier in the mixed impregnation liquid is 2wt%, heating to 82 ℃, reacting for 3h, drying under reduced pressure, and roasting the solid at 780 ℃ for 4h to obtain W @ Al2O3A catalyst.
Comparative example 3
The differences from example 3 are: using conventional Al2O3The nanoparticles act as a carrier.
Step 1, slowly dropping 6mol/L ammonia water into 1mol/LAl (NO)3)3In an aqueous solution, until the pH = 9-10, generating an aluminum hydroxide precipitate, then refluxing in an oil bath at 90 ℃ for 12h, repeatedly washing and filtering the precipitate with deionized water until the pH =7, and drying a filter cake at 110 ℃ to obtain Al2O3The nano particles are used as a carrier;
step 2, preparing Ir nano particle sol: adding H into 0.4mol/L dilute hydrochloric acid2IrCl6Let H stand for2IrCl6The concentration of the aqueous solution in dilute hydrochloric acid is 0.9wt%, the aqueous solution is heated for reaction, after the temperature is reduced, the pH value is adjusted to 6.5-7.5 by NaOH solution, Cetyl Trimethyl Ammonium Bromide (CTAB) is added into the solution, the concentration of the CTAB in the reaction solution is 12mmol/L, and 50mmol/L NaBH is added dropwise4Carrying out reduction reaction on the solution to obtain Ir nano particle sol;
step 3, loading of active center on the carrier: preparation of 1.6wt% H8N2O4W solution, adding Ir nano particle sol and H8N2O4The volume ratio of the W solution to the Ir nanoparticle sol was 4: 1, uniformly mixing to obtain a mixed impregnation liquid; adding Al into the mixed impregnating solution2O3Nanoparticles of Al2O3The concentration of the nano-particle carrier in the mixed impregnation liquid is 2wt%, the nano-particle carrier is heated to 82 ℃ to react for 3 hours, the mixture is decompressed and dried, and the solid is roasted for 4 hours at 780 ℃ to obtain W/Ir @ Al2O3A catalyst.
Comparative example 4
The differences from example 3 are: using conventional ZrO2The nanoparticles act as a carrier.
Step 1, slowly dropping 6mol/L ammonia water into 1mol/LZr (NO)3)4In an aqueous solution, until the pH is = 9-10, generating zirconium hydroxide precipitate, refluxing in an oil bath at 90 ℃ for 12 hours, repeatedly washing and filtering the precipitate with deionized water until the pH is =7, and drying a filter cake at 110 ℃ to obtain ZrO2The nano particles are used as a carrier;
step 2, preparing Ir nano particle sol: adding H into 0.4mol/L dilute hydrochloric acid2IrCl6Let H stand for2IrCl6The concentration of the aqueous solution in dilute hydrochloric acid is 0.9wt%, the aqueous solution is heated for reaction, after the temperature is reduced, the pH value is adjusted to 6.5-7.5 by NaOH solution, Cetyl Trimethyl Ammonium Bromide (CTAB) is added into the solution, the concentration of the CTAB in the reaction solution is 12mmol/L, and 50mmol/L NaBH is added dropwise4Carrying out reduction reaction on the solution to obtain Ir nano particle sol;
step 3, loading of active center on the carrier: preparation of 1.6wt% H8N2O4W solution, adding Ir nano particle sol and H8N2O4The volume ratio of the W solution to the Ir nanoparticle sol was 4: 1, uniformly mixing to obtain a mixed impregnation liquid; adding ZrO into the mixed impregnating solution2The nano-particles are used as a carrier to enable ZrO to be2The concentration of the nano-particle carrier in the mixed impregnation liquid is 2wt%, the nano-particle carrier is heated to 82 ℃ to react for 3 hours, the mixture is decompressed and dried, and the solid is roasted for 4 hours at 780 ℃ to obtain W/Ir @ Al2O3A catalyst.
Characterization test
FIG. 1 is an SEM photograph of hollow porous alumina microspheres prepared in example 3. As can be seen from the figure, the carrier has a hollow structure, and the surface thereof also has a porous structure. The XRD pattern is shown in figure 2, and the gamma-alumina crystal has the characteristics of gamma-alumina, has characteristic peaks at 67 degrees, 45.84 degrees, 37.59 degrees and 39.47 degrees, and has the characteristics of a cubic crystal system. MnO2The diffraction peaks at 37.4 ° and 66.7 ° are weaker and overlap with the gamma alumina diffraction peak. FIG. 3 is the W/Ir @ Al prepared in example 32O3The XRD pattern of the catalyst showed a diffraction peak of tungsten oxide at 22.8 deg. (denoted by W in the figure), and peaks of iridium oxide at 28.1 deg. and 54.0 deg. (denoted by I in the figure).
Alkylation reaction test
Isobutane and 2-butene were previously liquefied in a liquefied gas cylinder at an alkane/alkene ratio of 8: 1 as raw material gas. Pouring 4g of catalyst into a reaction kettle, removing air by using argon, adjusting the pressure of the reactor to 0.5MPa and 25 ℃, pumping 5L of raw material gas by using a high-pressure pump under the condition of vigorous stirring, reacting for 30min, collecting tail gas by using a gas collection bag,taking out the reaction solution to a measuring cylinder, standing, removing the catalyst at the bottom, analyzing the obtained alkylate oil, directly adding the catalyst at the bottom into a reaction kettle for alkylation reaction of fresh raw material gas, collecting the tail gas, and performing gas chromatography (SP6890, HP-PLOT Al)2O350 m.times.0.53 mm) under the following conditions: the sample inlet temperature is 200 ℃, the temperature of a chromatographic column box is 100 ℃, the detector is a hydrogen Flame Ionization Detector (FID), the detector temperature is 200℃, the composition of the alkylate oil is measured by a gas chromatograph-mass spectrometer (HP6890/5975), the quantitative analysis adopts a gas chromatography (SHIMADZU GC2014, DB-petro100m multiplied by 0.25mm) area normalization method, and the chromatographic analysis conditions are as follows: the sample inlet temperature is 270 ℃, and the temperature program of the chromatographic column box is as follows: maintaining at 40 deg.C for 2min, increasing 2.0/deg.C min to 60 deg.C, increasing 1.0/deg.C min to 130 deg.C, increasing 2.0/deg.C min to 180 deg.C, maintaining for 13min, wherein the detector is hydrogen Flame Ionization Detector (FID), and the detector temperature is 270 deg.C.
The results of the alkylation reaction of the catalysts of the above examples and comparative examples are shown in the following table:
Figure 849022DEST_PATH_IMAGE001
as can be seen from the table, the catalyst prepared by the invention has higher reaction activity in the alkylation reaction process of applying isobutane-butene, and the proportion of C8 in the product is high; as can be seen from example 3 and comparative example 2, by loading Ir as an active center on the catalyst support, the ratio of Ir to the C8 product in the reaction process can be effectively increased, and higher reaction activity is achieved; in addition, the octane number of the product obtained by the catalyst is superior to that of the solid acid catalyst which directly adopts granular alumina and zirconia as carriers in the prior art.
At H2In the SO4 catalytic process, the formation of "red oil" soluble in the catalyst, which finally results in the decrease of the catalyst activity, was separated and used directly in the next cyclic alkylation reaction, and in 8 reactions, the C8% of the product was as shown in the following table, and the C8 content was as shown in fig. 4:
Figure 628759DEST_PATH_IMAGE002
as can be seen from the table, the catalyst provided by the invention still has good reaction activity after 8 times of cyclic alkylation tests, the proportion of C8 is high, and the problem of catalyst deactivation can be effectively avoided after Mn is loaded in the preparation of the carrier as can be seen from the example 3 and the comparative example 1.

Claims (7)

1. A preparation method of a tungsten-based catalyst is characterized by comprising the following steps:
step 1, preparing monodisperse polystyrene-methacrylic acid composite microspheres: mixing 5-8 parts by weight of styrene, 1-1.5 parts by weight of divinylbenzene and 0.3-0.6 part by weight of methacrylic acid, adding 0.3-0.5 part by weight of dibenzoyl peroxide as an initiator, uniformly stirring, adding the mixture into 8-12 parts by weight of aqueous solution of polyvinyl alcohol with the concentration of 2-4 wt%, dispersing at a high speed, heating to perform a first reaction, adding sodium dodecyl benzene sulfonate into the reaction solution to enable the concentration of the sodium dodecyl benzene sulfonate in the reaction solution to be 0.3-0.5 wt%, heating to perform a second reaction, centrifugally separating a polymerization product, washing with deionized water, and drying in vacuum to obtain monodisperse polystyrene-methacrylic acid composite microspheres;
step 2, the surface of the microsphere is subjected to charge treatment: dispersing 2-5 parts of monodisperse polystyrene-methacrylic acid composite microspheres in 1-3 wt% of NaOH solution by weight, heating, centrifugally separating the product, washing with deionized water, and drying in vacuum to obtain microspheres with surface charges;
and 3, loading Mn on the surface of the microsphere: dispersing 1-3 parts by weight of surface-charged microspheres and 2-4 parts by weight of manganese sulfate in 300-400 parts by weight of deionized water, keeping the mixture at the temperature of 20-30 ℃ for 12-20 hours, and centrifugally separating the product to obtain Mn loaded on the surface2+The microspheres of (1);
step 4, preparing a hollow porous microsphere carrier: loading Mn on the surface in parts by weight2+Uniformly mixing 1-3 parts of the microspheres, 30 parts of deionized water and 120-150 parts of ethanol, adding 2-4 parts of aluminum nitrate and 0.5-0.8 part of urea, adjusting the pH to 7.5-8 by using 5-10 wt% of ammonia water, reacting at 25-35 ℃ for 12-24 hours, centrifugally separating precipitates, washing by using deionized water, drying in vacuum, and roasting the product to obtain a hollow porous alumina microsphere carrier;
and 5, preparing Ir nano particle sol: adding H into 0.3-0.6 mol/L dilute hydrochloric acid2IrCl6Let H stand for2IrCl6The concentration of the aqueous solution in dilute hydrochloric acid is 0.8-1.1 wt%, heating for reaction, cooling, adjusting the pH to 6.5-7.5 with NaOH solution, adding Cetyl Trimethyl Ammonium Bromide (CTAB) into the solution to make the concentration of CTAB in the reaction solution be 8-15 mmol/L, and then dropwise adding 40-60 mmol/L NaBH4Carrying out reduction reaction on the solution to obtain Ir nano particle sol;
step 6, loading of active center on the carrier: preparing 1.2-1.8 wt% of H8N2O4Adding Ir nano particle sol into the solution W, and uniformly mixing to obtain a mixed impregnation solution; adding a hollow porous alumina microsphere carrier into the mixed impregnation liquid to enable the concentration of the hollow porous alumina microsphere carrier in the mixed impregnation liquid to be 1-4 wt%, heating to 80-85 ℃, reacting for 2-4 h, drying under reduced pressure, and roasting the solid to obtain W/Ir @ Al2O3A catalyst;
in the 6 th step, H8N2O4The volume ratio of the W solution to the Ir nanoparticle sol is 3-6: 1, roasting is carried out at 750-800 ℃ for 2-5 h.
2. The method for preparing the tungsten-based catalyst according to claim 1, wherein in the step 1, the first reaction is carried out at 75-80 ℃ for 1-1.5 h, and the second reaction is carried out at 90-95 ℃ for 0.5-1 h.
3. The method for preparing a tungsten-based catalyst according to claim 1, wherein the temperature-raising treatment in the step 2 is a treatment at 40 to 45 ℃ for 0.5 to 1.5 hours.
4. The method for preparing the tungsten-based catalyst according to claim 1, wherein in the step 4, the roasting is carried out at 650-750 ℃ for 2-4 h.
5. W/Ir @ Al obtained by the process for preparing a tungsten-based catalyst according to any one of claims 1 to 42O3A catalyst.
6. A method for preparing isooctane by alkylation of isobutane-butene is characterized by comprising the following steps: W/Ir @ Al as claimed in claim 52O3In the presence of a catalyst, isobutane and 2-butene react in a reactor to obtain isooctane.
7. The method for preparing isooctane by alkylation of isobutane-butene according to claim 6, wherein the alkane/alkene ratio of isobutane to 2-butene is 7-10: 1, the reaction temperature is 25-40 ℃, and the reaction pressure is 0.40-0.50 MPa.
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