WO2023142258A1 - Preparation method for modified zsm-5 gold-loaded catalyst and use thereof - Google Patents

Preparation method for modified zsm-5 gold-loaded catalyst and use thereof Download PDF

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WO2023142258A1
WO2023142258A1 PCT/CN2022/083641 CN2022083641W WO2023142258A1 WO 2023142258 A1 WO2023142258 A1 WO 2023142258A1 CN 2022083641 W CN2022083641 W CN 2022083641W WO 2023142258 A1 WO2023142258 A1 WO 2023142258A1
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zsm
gold
catalyst
molecular sieve
modified
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祁彩霞
吴磊
孙立波
苏慧娟
孙逊
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烟台大学
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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
    • B01J29/42—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 containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B01J2229/126—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation in order to reduce the pore-mouth size
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a preparation method and application of a modified ZSM-5 loaded gold catalyst.
  • it relates to a method for preparing a catalyst by using a modified ZSM-5 molecular sieve to carry gold through a two-step method and the application of the catalyst in catalytic cracking to increase the production of propylene, belonging to the technical field of acid-metal bifunctional catalysts and their applications.
  • Propylene is mainly used to produce polypropylene, butanol, propylene oxide, etc., and polypropylene is the most important downstream product of propylene, and its demand growth is sufficient to represent the overall demand growth of propylene.
  • propylene is mainly divided into three major routes, steam cracking, catalytic cracking and propane dehydrogenation.
  • About 61% of the world's propylene comes from the by-products of steam cracking to produce ethylene, about 34% comes from the by-products of catalytic cracking in refineries to produce gasoline and diesel, about 3% comes from propane dehydrogenation units, and about 2% comes from other devices.
  • steam cracking has been the main source of light olefins and dienes.
  • the yields of ethylene and propylene range from 24% to 55% and 1.5% to 1.8%, respectively. main factor of the rate.
  • Steam cracking requires a high reaction temperature of 800-880 °C, and the annual energy consumption accounts for 40% of the total energy consumption in the petrochemical industry, and results in a large amount of CO 2 emissions.
  • the type of feedstock it uses limits the ability of steam cracking to control the ratio of propylene to ethylene in the production of light olefins, which is not in line with the current trend of propylene demand growth rate exceeding ethylene.
  • Catalytic dehydrogenation of propane to propylene can produce more propylene than hydrocarbon steam cracking. Although this production technology has been paid more and more attention, it is still limited by propane raw material resources to a certain extent.
  • the catalytic cracking reaction temperature is mostly at 550 ⁇ 650 In the range of °C, the propylene selectivity is high, and the device adaptability is strong. Therefore, the catalytic cracking process is playing an increasingly important role in increasing the production of propylene.
  • the catalytic cracking reaction using solid acid as a catalyst can control the product distribution by adjusting the acid amount, acid strength, acid type and acid distribution to achieve high propylene selectivity.
  • the ZSM-5 molecular sieve with double ten-membered ring structure exhibits excellent shape-selective catalytic ability due to its special pore structure.
  • the ratio of SiO 2 /Al 2 O 3 can be adjusted to make it have different acid properties.
  • ZSM-5 molecular sieve also exhibits good hydrothermal stability and strong anti-carbon deposition ability.
  • the modification of ZSM-5 molecular sieve has been widely studied. The modification method affects the physical and chemical properties of the catalyst, thereby affecting its catalytic performance, such as high temperature water vapor treatment (Phys. Chem. Chem. Phys. 2019, 21, 18758-18768), alkali Treatment (Catal. Lett.
  • Nanogold was first used in CO oxidation (Chem. Lett. 1987, 16, 405-408) and acetylene hydrochlorination (J. Catal. 1985, 96, 292-295), showing good low-temperature catalytic activity and the product Advantages of high selectivity. Then it is widely used in propylene epoxidation, water gas shift reaction, selective hydrogenation, etc.
  • Patent CN103143385A (2013) also reported that small-sized gold nanoparticles were loaded on high-silica zeolite molecular sieves including ZSM-5 by negative pressure deposition and precipitation method, in propane (or a mixture of propane and butane with a propane content higher than 50%, Or oilfield liquefied gas) dehydrogenation to olefins reaction shows a high conversion of propane and selectivity of olefins and aromatics.
  • the technical problem to be solved by the present invention is to provide a preparation method and application of a modified ZSM-5 gold-supported catalyst, which exhibits more excellent cracking activity, propylene selectivity and performance, catalytic stability, and can greatly reduce the reaction temperature.
  • modified ZSM-5 loaded gold catalyst is characterized in that comprising ZSM-5 modified and nano-gold loaded steps:
  • the ZSM-5 molecular sieve matrix is treated by the external surface modification method, including the following steps: take the roasted ZSM-5 molecular sieve in the modifier solution, ultrasonically disperse it evenly, stir at a constant temperature, wash the obtained suspension with absolute ethanol, and dry to constant weight; or,
  • Treating the ZSM-5 molecular sieve matrix with ammonium hexafluorosilicate includes the following steps: take the roasted ZSM-5 molecular sieve and place it in an ammonium acetate buffer solution, stir, add ammonium hexafluorosilicate solution, continue stirring, cooling, Centrifugal washing, drying to constant weight and roasting;
  • step (1) supports nano-gold to obtain a catalyst; the theoretical gold loading of the catalyst is 0.1 ⁇ 0.5 wt%.
  • the step (2) can adopt the gold sol adsorption method, adding the modified ZSM-5 molecular sieve into the gold sol, stirring and adsorbing.
  • the preparation method of the gold sol is as follows: heating the HAuCl 4 solution to boiling; then adding sodium citrate solution, waiting until the solution turns wine red, continuing to boil, and cooling.
  • the molar ratio of the sodium citrate to HAuCl is preferably 2-10; the boiling time is preferably 20-50 min.
  • the step (2) can also use Au(en) 2 Cl 3 as the gold precursor;
  • the preparation method of the (Au(en) 2 Cl 3 ) is: add ethylenediamine solution to the HAuCl 4 solution under stirring, After continuing to stir evenly, absolute ethanol was added dropwise, and the stirring was continued. The resulting suspension was centrifuged, washed with absolute ethanol, and dried to obtain Au(en) 2 Cl 3 .
  • the mass ratio of the HAuCl 4 to ethylenediamine is preferably 10-30; the mass ratio of the absolute ethanol to HAuCl 4 is preferably 10-20.
  • the step (2) can also use HAuCl 4 solution as the gold precursor.
  • the preferred modifying agent is a modifying agent having a molecular size greater than the pore diameter including octadecyltrimethoxysilane and dodecyltrimethoxysilane; the mass ratio of the ZSM-5 to the modifying agent is preferably 0.5 to 20 ; The mass concentration of the modifier is preferably 0.01 to 0.2.
  • the molar ratio of the ammonium hexafluorosilicate to Al in the ZSM-5 molecular sieve is preferably 0.5-2; the molar ratio of the ammonium acetate to ammonium hexafluorosilicate is preferably 100-200.
  • the modified ZSM-5 gold-carrying catalyst is used for preparing propylene by catalytic cracking of n-octane or catalytic cracking of light oil to prepare propylene.
  • the present invention uses the advantages of nano-gold, firstly optimizes the molecular sieve carrier, and then prepares a high-performance catalytic cracking ZSM-5 gold-loaded dual-function catalyst by a two-step method of loading gold, which realizes At a reaction temperature lower than 100 °C or even 150 °C, the catalytic effect is similar to that of its parent ZSM-5, which shows great energy-saving potential and reduces environmental pollution.
  • the method has simple operation, mild conditions, high reproducibility of the obtained catalyst, and good industrial application prospect.
  • the pore diameter of the molecular sieve can be effectively reduced without affecting the internal pore structure of the molecular sieve; the present invention greatly improves the strength of B acid through the dealumination in the presence of buffer solution, Then gold nanoparticles are introduced, which greatly improves the selectivity of propylene compared with the unmodified parent ZSM-5 at the same reaction temperature; the catalytic performance is reduced by 100 or even 150 °C and is similar to that of the parent ZSM-5.
  • the loading of Au in the obtained catalyst is low (0.1% ⁇ 0.5%).
  • the present invention adopts a two-step method of molecular sieve modification (external surface modification or dealumination in the presence of a buffer) and molecular sieve modified to support nano-gold to prepare a catalyst for catalytic cracking of n-octane or light diesel oil to prepare propylene.
  • the post-treatment series of molecular sieves mainly affect the catalytic cracking performance from the pore size (shape-selective ability) and acidity (cracking ability) of the molecular sieve, affecting the reaction path and final product.
  • the introduction of nano-gold further improves the pore structure of molecular sieves and strengthens B acid, which not only improves the cracking ability of positive carbon particles, but also plays a certain role in the dehydrogenation of hydrocarbons.
  • the modified ZSM-5 gold-supported catalyst prepared by the present invention has unique technical advantages in catalytic cracking to increase the production of propylene, and is more conducive to market promotion.
  • Fig. 1 is the distribution diagram (1) of the molecular sieve pores of the ZSM-5 gold-loaded catalyst prepared by the external surface modification method of Example 2 of the present invention, keeping the gold loading of 0.1wt%, and the concentration of octadecyltrimethoxysilane from 1% ⁇ 4wt%, in the figure a: ZSM-5; b: ZSM-5-1%TOS;c:0.1%Au/ZSM-5-1%TOS;d:0.1%Au/ZSM-5-2% TOS; e: 0.1%Au/ZSM-5-3%TOS; f: 0.1%Au/ZSM-5-4%TOS.
  • Fig. 2 is the molecular sieve pore distribution diagram (two) of the ZSM-5 loaded gold catalyst prepared by the external surface modification method in Example 2 of the present invention, keeping the concentration of 1wt% octadecyltrimethoxysilane, and the loading of gold nanoparticles
  • the amount is from 0.1% to 0.5wt%, in the figure a: ZSM-5;b:ZSM-5-1%TOS;c:0.1%Au/ZSM-5-1%TOS;d:0.2%Au/ZSM-5-1%TOS;e:0.3%Au/ZSM- 5-1%TOS; f: 0.4%Au/ZSM-5-1%TOS; g: 0.5%Au/ZSM-5-1%TOS.
  • Fig. 3 is the n-octane catalytic cracking performance evaluation diagram (1) of Au/ZSM-5-TOS series catalysts in Example 3 of the present invention; The conversion rate of n-octane under the concentration of trimethoxysilane from 1% to 4wt%.
  • Fig. 4 is the n-octane catalytic cracking performance evaluation diagram (two) of Au/ZSM-5-TOS series catalysts in Example 3 of the present invention; Propylene selectivity under the concentration of trimethoxysilane from 1% to 4wt%.
  • Fig. 5 is the n-octane catalytic cracking performance evaluation diagram (three) of Au/ZSM-5-TOS series catalysts in Example 3 of the present invention; Concentration, loading of gold nanoparticles from 0.1% to 0.5wt% n-octane conversion.
  • Fig. 6 is the n-octane catalytic cracking performance evaluation figure (four) of Au/ZSM-5-TOS series catalyst in the embodiment of the present invention 3; Concentration, propylene selectivity under loading of gold nanoparticles from 0.1% to 0.5wt%.
  • Fig. 9 is the transmission electron micrograph (a) and the element map (b) of the 0.3%Au/ZSM-5-F catalyst in Example 5 of the present invention.
  • Figure 10 is an evaluation chart (1) of n-octane catalytic cracking performance of Au/ZSM-5-F series catalysts under the conditions of Example 6 of the present invention, and Figure 10 is used to show n-octane conversion.
  • Figure 11 is the n-octane catalytic cracking performance evaluation chart (2) of Au/ZSM-5-F series catalysts under the conditions of Example 6 of the present invention, and Figure 11 is used to show the propylene selectivity.
  • Figure 12 is a diagram of the stability test results of the Au/ZSM-5-F catalyst in Example 8 of the present invention.
  • Fig. 13 is a transmission electron microscope image of the Au/ZSM-5-F catalyst in Example 9 of the present invention.
  • Figure 1 and Figure 2 are the pore diameter distribution diagrams of the catalyst prepared under the conditions of this example. It can be seen from the figure that the pore structure of the modified catalyst is more regular, which is more conducive to the production of propylene by shape-selective catalysis.
  • Example 3 Application of the ZSM-5 gold-supported catalyst prepared by the external surface modification method in the catalytic cracking of n-octane to increase the production of propylene .
  • the evaluation of the Au/ZSM-5-TOS series catalysts was carried out in a custom-made catalytic cracking micro-reaction tube.
  • the reaction temperature was 260-460 °C. 3 g of catalyst was loaded into the reaction tube.
  • 0.94 g of n-octane was injected into the reactor tube through a syringe and reacted for 70 s.
  • the gas bag collects gas phase products
  • the colorimetric tube collects liquid phase products.
  • the reaction products were analyzed by chromatography using a GC-920(X) with an OV-101 capillary column and a hydrogen flame ionization detector.
  • Figure 3 to Figure 6 are the n-octane catalytic cracking performance evaluation of Au/ZSM-5-TOS series catalysts under the conditions of this example. It can be seen from the figure that the 0.2%Au/ZSM-5-1%TOS catalyst reduces the reaction temperature by more than 100°C while realizing the complete conversion of n-octane.
  • Example 4 Prepared by surface modification ZSM-5 Application of supported gold catalyst in catalytic cracking of light oil to increase propylene production
  • the evaluation of 0.2%Au/ZSM-5-1%TOS series catalysts was carried out in a custom-made catalytic cracking micro-reaction tube.
  • the reaction temperature is 260 ⁇ 460 °C, 3g of catalyst is packed in the reaction tube, when the temperature reaches the preset temperature, 0.94g of light diesel oil is injected into the reactor tube through the syringe, and reacted for 70s.
  • the gas bag collects gas phase products, and the colorimetric tube collects liquid phase products.
  • the reaction products were analyzed by chromatography using a GC-920(X) with an OV-101 capillary column and a hydrogen flame ionization detector.
  • Table 1 is an evaluation table of the light diesel oil catalytic cracking performance of the catalyst under the conditions of this example. It can be seen from the table that the conversion of light oil and the selectivity of propylene of the modified catalyst both show certain advantages.
  • the solution was cooled to room temperature, it was washed by centrifugation, dried to constant weight and then calcined to obtain ZSM-5-F catalyst (the catalyst of the control group was named ZSM-5-N without adding buffer solvent), and then loaded with different concentrations of Au by equal volume impregnation method (en) 2 Cl 3 , the immersion time is not less than 24 h, washed and dried to constant weight, and roasted at 550 °C.
  • Figure 7 and Figure 8 are the pyridine adsorption diagrams of the catalyst prepared under the conditions of this example. It can be seen from the figure that the B acid content and strength of the modified catalyst increase, and the enhancement of B acid helps the cracking reaction to occur.
  • Fig. 9 is a transmission electron microscope image (a) and an elemental map (b) of the catalyst prepared under the conditions of this example. It can be seen from the figure that fewer Au nanoparticles are deposited on the surface of the molecular sieve, and the results of elemental mapping reflect that the unobserved small-sized gold may enter the pores of the analytical sieve, which can also be inferred from the pore size distribution figure. result.
  • Example 6 prepared by dealumination ZSM-5 Application of Gold-supported Catalyst in Catalytic Cracking of n-Octane to Increase Production of Propylene
  • Figure 10 and Figure 11 are evaluation diagrams of n-octane catalytic cracking performance of Au/ZSM-5-F series catalysts under the conditions of this example. It can be seen from the figure that the 0.3%Au/ZSM-5-F catalyst reduces the reaction temperature by more than 150°C while realizing the complete conversion of n-octane.
  • Example 7 prepared by dealumination ZSM-5 Application of supported gold catalyst in catalytic cracking of light oil to increase propylene production
  • Table 2 is an evaluation table of the light diesel oil catalytic cracking performance of the catalyst under the conditions of the examples. It can be seen from the table that the conversion of light oil and the selectivity of propylene of the modified catalyst both show certain advantages.
  • Example 8 prepared by dealumination ZSM-5 Stability test of gold-supported catalyst in n-octane catalytic cracking to increase propylene production
  • Figure 12 is a diagram of the stability test results of the Au/ZSM-5-F catalyst. It can be seen from the figure that the n-octane conversion rate and propylene output of the modified catalyst fluctuate within a certain range, and there is no obvious decrease after 15 cycles.
  • Example 9 prepared by the gold sol method ZSM-5 gold catalyst
  • HAuCl 4 solution Take a certain amount of HAuCl 4 solution, add an appropriate amount of deionized water, and heat to vigorous boiling. Quickly add a certain amount of sodium citrate solution, the molar ratio of sodium citrate to HAuCl4 is 5, wait until the solution turns wine red, continue to boil for 20min, and cool down to room temperature naturally. Add the above-mentioned ZSM-5-F catalyst, stir and adsorb for 24 hours, then wash and dry, and the theoretical gold loading is 0.5wt%.
  • Figure 13 is a transmission electron microscope image of the Au/ZSM-5-F catalyst. It can be seen from the figure that the gold sol method can better control the size of gold nanoparticles and make the dispersion of gold nanoparticles more uniform.
  • the Au/ZSM-5 catalyst can be prepared by a deposition-precipitation method, and the pH value of the deposition-precipitation method needs to be controlled to be 9-10, or the gold nanoparticles are loaded on the ZSM-5 molecular sieve by the impregnation method, which needs to be impregnated for more than 24 h, or The gold sol adsorption method was adopted, and the adsorption time was controlled above 24 h.
  • the theoretical gold loading mass percentage of the catalyst is 0.1%-0.5%.

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Abstract

Disclosed in the present invention are a preparation method for a modified ZSM-5 gold-loaded catalyst and the use thereof. Provided are a two-step method for preparing, by means of loading gold on ZSM-5, a bi-functional catalyst having a high performance catalytic cracking action, and the use thereof. First, the outer surface of a ZSM-5 molecular sieve is modified by means of a modifier to reduce the pore opening size of the molecular sieve or aluminum removal treatment is carried out in the presence of a buffer to increase B acid intensity and content, thereby effectively adjusting the pore diameter and acidity of the molecular sieve without changing the pore structure of the molecular sieve. Then, gold nanoparticles are loaded on the modified molecular sieve. The prepared catalyst shows excellent low-temperature catalytic activity and propylene selectivity in propylene yield increase by means of catalytic cracking of hydrocarbon such as light diesel oil, n-octane and the like. The obtained catalyst can achieve a catalytic effect similar to that of a parent ZSM-5 under a temperature difference with the reaction temperature less than 100 ℃ or even 150 ℃, shows huge energy-saving potential, and also reduces environmental pollution. The series of catalysts achieve low-temperature high yield of propylene because of the dual effects of low gold loading amount and molecular sieve modification.

Description

修饰ZSM-5载金催化剂的制备方法及应用Preparation method and application of modified ZSM-5 supported gold catalyst 技术领域technical field
本发明涉及修饰ZSM-5载金催化剂的制备方法及应用。特别涉及一种利用修饰的ZSM-5分子筛载金并通过两步法制备催化剂的方法及所述催化剂在催化裂化增产丙烯中的应用，属于酸与金属双功能催化剂及其应用技术领域。The invention relates to a preparation method and application of a modified ZSM-5 loaded gold catalyst. In particular, it relates to a method for preparing a catalyst by using a modified ZSM-5 molecular sieve to carry gold through a two-step method and the application of the catalyst in catalytic cracking to increase the production of propylene, belonging to the technical field of acid-metal bifunctional catalysts and their applications.
背景技术Background technique
随着全球消费结构的不断变化，人们对丙烯的各类深加工产品的需求持续增长，其中亚太地区的需求增速最快，远远领先全球其他地区需求量。丙烯主要用于生产聚丙烯、丁辛醇、环氧丙烷等，而聚丙烯作为丙烯下游最主要的产品，其需求量的增长足以代表丙烯整体需求增长。With the continuous changes in the global consumption structure, people's demand for various deep-processing products of propylene continues to grow, and the demand in the Asia-Pacific region has the fastest growth rate, far ahead of the demand in other regions of the world. Propylene is mainly used to produce polypropylene, butanol, propylene oxide, etc., and polypropylene is the most important downstream product of propylene, and its demand growth is sufficient to represent the overall demand growth of propylene.
目前丙烯的生产主要分为三大路径，蒸汽裂解，催化裂化和丙烷脱氢。世界上约61 %的丙烯来自蒸汽裂解生产乙烯的副产品,约34 %来自炼油厂催化裂化生产汽、柴油的副产品,约3 %来自丙烷脱氢装置,约2 %来自其它装置。At present, the production of propylene is mainly divided into three major routes, steam cracking, catalytic cracking and propane dehydrogenation. About 61% of the world's propylene comes from the by-products of steam cracking to produce ethylene, about 34% comes from the by-products of catalytic cracking in refineries to produce gasoline and diesel, about 3% comes from propane dehydrogenation units, and about 2% comes from other devices.
半个多世纪以来，蒸汽裂解一直是轻烯烃和二烯烃的主要来源，其乙烯和丙烯的产率分别在24%~55%和1.5%~1.8%之间，原料种类和操作条件是影响产率的主要因素。蒸汽裂解需要800~880 ℃的高反应温度，每年消耗的能量占石油化工行业消耗总能量的40 %，且导致大量的CO 2排放。另外其所使用的原料种类限制了蒸汽裂解在轻烯烃生产过程中控制丙烯与乙烯比率的能力，这不符合当前丙烯需求增长率超过乙烯的趋势要求。 For more than half a century, steam cracking has been the main source of light olefins and dienes. The yields of ethylene and propylene range from 24% to 55% and 1.5% to 1.8%, respectively. main factor of the rate. Steam cracking requires a high reaction temperature of 800-880 ℃, and the annual energy consumption accounts for 40% of the total energy consumption in the petrochemical industry, and results in a large amount of CO 2 emissions. In addition, the type of feedstock it uses limits the ability of steam cracking to control the ratio of propylene to ethylene in the production of light olefins, which is not in line with the current trend of propylene demand growth rate exceeding ethylene.
丙烷催化脱氢制丙烯比烃类蒸气裂解能产生更多的丙烯，虽然该生产技术日益受到重视，但一定程度上仍受丙烷原料资源的限制。而催化裂化反应温度大都在550~650 ℃范围内，其丙烯选择性较高，装置适应能力强。所以催化裂化工艺在增产丙烯方面正发挥越来越重要的作用。以固体酸为催化剂的催化裂化反应可通过调节酸量、酸强度、酸种类以及酸分布，来控制产物分布，以实现高的丙烯选择性。Catalytic dehydrogenation of propane to propylene can produce more propylene than hydrocarbon steam cracking. Although this production technology has been paid more and more attention, it is still limited by propane raw material resources to a certain extent. The catalytic cracking reaction temperature is mostly at 550~650 In the range of ℃, the propylene selectivity is high, and the device adaptability is strong. Therefore, the catalytic cracking process is playing an increasingly important role in increasing the production of propylene. The catalytic cracking reaction using solid acid as a catalyst can control the product distribution by adjusting the acid amount, acid strength, acid type and acid distribution to achieve high propylene selectivity.
具有双十元环结构的ZSM-5分子筛由于其特殊的孔结构，表现出优异的择形催化能力。可通过调节SiO 2/Al 2O 3的比例，使其具有不同的酸性质，除此之外，ZSM-5分子筛还表现出良好的水热稳定性以及较强的抗积碳能力。ZSM-5分子筛改性已被广泛研究，改性方式影响催化剂的物理化学性质，从而影响其催化性能，例如高温水汽处理（Phys. Chem. Chem. Phys. 2019, 21, 18758-18768），碱处理（Catal. Lett. 2003, 91, 155-167），元素改性（Microporous. Mesoporous. Mater. 2019, 284, 316-326）等。纳米金最早被使用在CO氧化（Chem. Lett. 1987, 16, 405-408），乙炔氢氯化反应中（J. Catal. 1985, 96, 292-295），表现出低温催化活性好，产物选择性高等优点。随后被广泛使用在丙烯环氧化，水煤气变换反应，选择性加氢等。 The ZSM-5 molecular sieve with double ten-membered ring structure exhibits excellent shape-selective catalytic ability due to its special pore structure. The ratio of SiO 2 /Al 2 O 3 can be adjusted to make it have different acid properties. In addition, ZSM-5 molecular sieve also exhibits good hydrothermal stability and strong anti-carbon deposition ability. The modification of ZSM-5 molecular sieve has been widely studied. The modification method affects the physical and chemical properties of the catalyst, thereby affecting its catalytic performance, such as high temperature water vapor treatment (Phys. Chem. Chem. Phys. 2019, 21, 18758-18768), alkali Treatment (Catal. Lett. 2003, 91, 155-167), element modification (Microporous. Mesoporous. Mater. 2019, 284, 316-326), etc. Nanogold was first used in CO oxidation (Chem. Lett. 1987, 16, 405-408) and acetylene hydrochlorination (J. Catal. 1985, 96, 292-295), showing good low-temperature catalytic activity and the product Advantages of high selectivity. Then it is widely used in propylene epoxidation, water gas shift reaction, selective hydrogenation, etc.
发明人所在实验室之前的工作（祁彩霞，刘从华，等.中国发明专利；CN103143387A）(Chinese. J. Catal. 2016, 37, 1747-1754)证明在ZSM-5分子筛中引入Au纳米粒子可在一定程度上降低轻柴油催化裂化反应温度，并在不同程度上提高反应的转化率，微反活性和丙烯选择性。通过在催化剂中负载适量的La，不仅稳定了金纳米粒子，防止其团聚，而且有效的提高了催化剂对轻柴油和正辛烷的催化裂化性能( Ind. Eng. Chem. Res. 2019, 58, 14695-14704)。实验室还发现金属态的金而不是显正价态的金对正辛烷催化裂化有利（J. Phys. Chem. C, 2021, 125, 16013-16023），郭等人也发现金纳米粒子的加入可提高 Zn/HZSM-5催化剂对正丁烷的脱氢和芳构化性能，其烯烃选择性和芳烃的选择性有所提高（Chinese. J. Catal, 2013, 34, 1262-1266）。专利CN103143385A（2013）也报道了小尺寸金纳米粒子以负压沉积沉淀法负载到包括ZSM-5等高硅沸石分子筛上，在丙烷（或丙烷含量高于50 %的丙烷和丁烷的混合物，或油田液化气）脱氢制烯烃反应表现出较高的丙烷转化率和烯烃及芳烃选择性。Previous work of the inventor's laboratory (Qi Caixia, Liu Conghua, etc. Chinese invention patent; CN103143387A) (Chinese. J. Catal. 2016, 37, 1747-1754) proved that the introduction of Au nanoparticles into ZSM-5 molecular sieves can reduce the catalytic cracking reaction temperature of light oil to a certain extent, and improve the conversion rate of the reaction, microreaction activity and propylene selectivity to varying degrees. By loading an appropriate amount of La in the catalyst, it not only stabilizes the gold nanoparticles and prevents them from agglomerating, but also effectively improves the catalytic cracking performance of the catalyst for gas oil and n-octane (Ind. Eng. Chem. Res. 2019, 58, 14695-14704). The laboratory also found that gold in the metallic state, rather than in the positively valent state, favored n-octane catalytic cracking (J. Phys. Chem. C, 2021, 125, 16013-16023), Guo et al. also found that the addition of gold nanoparticles can improve The performance of Zn/HZSM-5 catalyst for dehydrogenation and aromatization of n-butane, and its olefin selectivity and aromatics selectivity were improved (Chinese. J. Catal, 2013, 34, 1262-1266). Patent CN103143385A (2013) also reported that small-sized gold nanoparticles were loaded on high-silica zeolite molecular sieves including ZSM-5 by negative pressure deposition and precipitation method, in propane (or a mixture of propane and butane with a propane content higher than 50%, Or oilfield liquefied gas) dehydrogenation to olefins reaction shows a high conversion of propane and selectivity of olefins and aromatics.
以上工作虽都证明了纳米金在烃类催化裂化制烯烃上都表现出了提高烯烃产率和降低反应温度的效果，但在反应温度上的降低和丙烯选择上的提高仍有较大空间去改善。Although the above work has proved that nano-gold has the effect of increasing the yield of olefins and reducing the reaction temperature in the catalytic cracking of hydrocarbons to olefins, there is still a lot of room for the reduction of reaction temperature and the improvement of propylene selection. improve.
技术问题technical problem
本发明所要解决的技术问题是，提供一种修饰ZSM-5载金催化剂的制备方法及应用，所述催化剂在正辛烷和轻柴油催化裂化反应中表现出更为优异的裂化活性、丙烯选择性、催化稳定性，并能够大幅度降低反应温度。The technical problem to be solved by the present invention is to provide a preparation method and application of a modified ZSM-5 gold-supported catalyst, which exhibits more excellent cracking activity, propylene selectivity and performance, catalytic stability, and can greatly reduce the reaction temperature.
技术解决方案technical solution
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
修饰ZSM-5载金催化剂的制备方法，其特征在于包括ZSM-5修饰和纳米金负载步骤：The preparation method of modified ZSM-5 loaded gold catalyst is characterized in that comprising ZSM-5 modified and nano-gold loaded steps:
（一）ZSM-5修饰方法(1) ZSM-5 modification method
（1）外表面修饰法处理ZSM-5分子筛母体，包括以下步骤：取焙烧后的ZSM-5分子筛于修饰剂溶液之中，超声分散均匀，恒温搅拌，所得悬浮液用无水乙醇洗涤，干燥至恒重；或者，(1) The ZSM-5 molecular sieve matrix is treated by the external surface modification method, including the following steps: take the roasted ZSM-5 molecular sieve in the modifier solution, ultrasonically disperse it evenly, stir at a constant temperature, wash the obtained suspension with absolute ethanol, and dry to constant weight; or,
（2）六氟硅酸铵处理ZSM-5分子筛母体，包括以下步骤：取焙烧后的ZSM-5分子筛置于醋酸铵缓冲溶液中，搅拌，加入六氟硅酸铵溶液，继续搅拌，冷却，离心洗涤，干燥至恒重后焙烧；(2) Treating the ZSM-5 molecular sieve matrix with ammonium hexafluorosilicate includes the following steps: take the roasted ZSM-5 molecular sieve and place it in an ammonium acetate buffer solution, stir, add ammonium hexafluorosilicate solution, continue stirring, cooling, Centrifugal washing, drying to constant weight and roasting;
（二）经过步骤（一）修饰的ZSM-5负载纳米金得到催化剂；所述催化剂的理论载金量为0.1~0.5 wt%。(2) The ZSM-5 modified by step (1) supports nano-gold to obtain a catalyst; the theoretical gold loading of the catalyst is 0.1~0.5 wt%.
所述步骤（二）可以采用金溶胶吸附法，将修饰后的ZSM-5分子筛加入到金溶胶中，搅拌吸附。The step (2) can adopt the gold sol adsorption method, adding the modified ZSM-5 molecular sieve into the gold sol, stirring and adsorbing.
所述金溶胶的制备方法为：将HAuCl 4溶液加热至沸腾；然后加入柠檬酸钠溶液，等到溶液变为酒红色后继续煮沸，冷却。 The preparation method of the gold sol is as follows: heating the HAuCl 4 solution to boiling; then adding sodium citrate solution, waiting until the solution turns wine red, continuing to boil, and cooling.
所述柠檬酸钠与HAuCl 4的摩尔比优选为2~10；所述的煮沸时长优选为20~50 min。 The molar ratio of the sodium citrate to HAuCl is preferably 2-10; the boiling time is preferably 20-50 min.
所述步骤（二）也可以以Au(en) 2Cl 3作为金前驱体；所述（Au(en) 2Cl 3）的制备方法为：搅拌下向HAuCl 4溶液中加入乙二胺溶液，继续搅拌均匀后滴加无水乙醇，再继续搅拌，所得悬浊液离心分离，无水乙醇洗涤，干燥得到Au(en) 2Cl 3。 The step (2) can also use Au(en) 2 Cl 3 as the gold precursor; the preparation method of the (Au(en) 2 Cl 3 ) is: add ethylenediamine solution to the HAuCl 4 solution under stirring, After continuing to stir evenly, absolute ethanol was added dropwise, and the stirring was continued. The resulting suspension was centrifuged, washed with absolute ethanol, and dried to obtain Au(en) 2 Cl 3 .
所述HAuCl 4与乙二胺的质量比优选为10~30；所述无水乙醇与HAuCl 4的质量比优选为10~20。 The mass ratio of the HAuCl 4 to ethylenediamine is preferably 10-30; the mass ratio of the absolute ethanol to HAuCl 4 is preferably 10-20.
所述步骤（二）还可以以HAuCl 4溶液作为金前驱体。 The step (2) can also use HAuCl 4 solution as the gold precursor.
优选的修饰剂为包括十八烷基三甲氧基硅烷和十二烷基三甲氧基硅烷在内的分子尺寸大于孔径的修饰剂；所述ZSM-5与修饰剂的质量比优选为0.5~20；所述修饰剂的质量浓度优选为0.01~0.2。The preferred modifying agent is a modifying agent having a molecular size greater than the pore diameter including octadecyltrimethoxysilane and dodecyltrimethoxysilane; the mass ratio of the ZSM-5 to the modifying agent is preferably 0.5 to 20 ; The mass concentration of the modifier is preferably 0.01 to 0.2.
所述的六氟硅酸铵与ZSM-5分子筛中Al的摩尔比优选为0.5~2；所述的醋酸铵与六氟硅酸铵的摩尔比优选为100~200。The molar ratio of the ammonium hexafluorosilicate to Al in the ZSM-5 molecular sieve is preferably 0.5-2; the molar ratio of the ammonium acetate to ammonium hexafluorosilicate is preferably 100-200.
所述修饰ZSM-5载金催化剂用于正辛烷催化裂化制备丙烯或者轻柴油催化裂化制备丙烯。The modified ZSM-5 gold-carrying catalyst is used for preparing propylene by catalytic cracking of n-octane or catalytic cracking of light oil to prepare propylene.
有益效果Beneficial effect
本发明的积极效果在于：本发明是在利用纳米金优点的同时，先对分子筛载体进行优化而后载金的两步法制备了高性能的催化裂化ZSM-5载金双功能催化剂，实现了可在反应温度低于100 ℃甚至150 ℃的温差下取得与其母体ZSM-5相近的催化效果，显示出巨大的节能潜力，同时也减少了环境污染。该方法操作简单，条件温和，所得催化剂重复性高，有良好的工业应用前景。The positive effects of the present invention are: the present invention uses the advantages of nano-gold, firstly optimizes the molecular sieve carrier, and then prepares a high-performance catalytic cracking ZSM-5 gold-loaded dual-function catalyst by a two-step method of loading gold, which realizes At a reaction temperature lower than 100 °C or even 150 °C, the catalytic effect is similar to that of its parent ZSM-5, which shows great energy-saving potential and reduces environmental pollution. The method has simple operation, mild conditions, high reproducibility of the obtained catalyst, and good industrial application prospect.
本发明通过对ZSM-5分子筛外表面修饰，可以在不影响分子筛内部孔道结构的情况下，有效地实现分子筛孔径的减小；本发明通过缓冲液存在下的脱铝大幅提高了B酸强度，然后引入金纳米粒子，在同一反应温度下与未改性的母体ZSM-5相比较大程度上提高了丙烯选择性；实现了降低100甚至150℃与母体ZSM-5相近的催化性能。所得催化剂中Au的负载量较低（0.1%~0.5%）。In the present invention, by modifying the outer surface of the ZSM-5 molecular sieve, the pore diameter of the molecular sieve can be effectively reduced without affecting the internal pore structure of the molecular sieve; the present invention greatly improves the strength of B acid through the dealumination in the presence of buffer solution, Then gold nanoparticles are introduced, which greatly improves the selectivity of propylene compared with the unmodified parent ZSM-5 at the same reaction temperature; the catalytic performance is reduced by 100 or even 150 °C and is similar to that of the parent ZSM-5. The loading of Au in the obtained catalyst is low (0.1%~0.5%).
本发明采用分子筛修饰（外表面修饰或者缓冲液存在下的脱铝修饰）与分子筛经修饰后负载纳米金的两步法制备用于正辛烷或者轻柴油催化裂化制备丙烯的催化剂，其在催化裂化活性、丙烯选择性、催化稳定性以及明显降低反应温度方面取得明显优于现有技术的效果。分子筛的系列后处理，主要从分子筛的孔径（择形能力）以及酸性（裂解能力）方面影响催化裂化性能，影响着反应路径及最终产物。纳米金的引入进一步完善分子筛孔道结构和增强B酸，在提高正碳粒子裂解能力的同时，在烃类的脱氢方面也起到了一定的作用。The present invention adopts a two-step method of molecular sieve modification (external surface modification or dealumination in the presence of a buffer) and molecular sieve modified to support nano-gold to prepare a catalyst for catalytic cracking of n-octane or light diesel oil to prepare propylene. In terms of activity, propylene selectivity, catalytic stability and significantly lower reaction temperature, the effect is significantly better than that of the prior art. The post-treatment series of molecular sieves mainly affect the catalytic cracking performance from the pore size (shape-selective ability) and acidity (cracking ability) of the molecular sieve, affecting the reaction path and final product. The introduction of nano-gold further improves the pore structure of molecular sieves and strengthens B acid, which not only improves the cracking ability of positive carbon particles, but also plays a certain role in the dehydrogenation of hydrocarbons.
综上所述，本发明制备的修饰ZSM-5载金催化剂在催化裂化增产丙烯中具有独特的技术优势，更有利于市场推广。In summary, the modified ZSM-5 gold-supported catalyst prepared by the present invention has unique technical advantages in catalytic cracking to increase the production of propylene, and is more conducive to market promotion.
附图说明Description of drawings
图1是本发明实施例2外表面修饰法制备的ZSM-5载金催化剂的分子筛孔经分布图（一）,保持0.1wt%的金负载量，十八烷基三甲氧基硅烷的浓度从1%~4wt%，图中a: ZSM-5; b: ZSM-5-1%TOS;c:0.1%Au/ZSM-5-1%TOS;d:0.1%Au/ZSM-5-2%TOS; e: 0.1%Au/ZSM-5-3%TOS; f: 0.1%Au/ZSM-5-4%TOS。Fig. 1 is the distribution diagram (1) of the molecular sieve pores of the ZSM-5 gold-loaded catalyst prepared by the external surface modification method of Example 2 of the present invention, keeping the gold loading of 0.1wt%, and the concentration of octadecyltrimethoxysilane from 1%~4wt%, in the figure a: ZSM-5; b: ZSM-5-1%TOS;c:0.1%Au/ZSM-5-1%TOS;d:0.1%Au/ZSM-5-2% TOS; e: 0.1%Au/ZSM-5-3%TOS; f: 0.1%Au/ZSM-5-4%TOS.
图2是本发明实施例2外表面修饰法制备的ZSM-5载金催化剂的分子筛孔经分布图（二）,保持1wt%的十八烷基三甲氧基硅烷的浓度，金纳米粒子的负载量从0.1%~0.5wt%，图中a: ZSM-5;b:ZSM-5-1%TOS;c:0.1%Au/ZSM-5-1%TOS;d:0.2%Au/ZSM-5-1%TOS;e: 0.3%Au/ZSM-5-1%TOS; f: 0.4%Au/ZSM-5-1%TOS; g: 0.5%Au/ZSM-5-1%TOS。Fig. 2 is the molecular sieve pore distribution diagram (two) of the ZSM-5 loaded gold catalyst prepared by the external surface modification method in Example 2 of the present invention, keeping the concentration of 1wt% octadecyltrimethoxysilane, and the loading of gold nanoparticles The amount is from 0.1% to 0.5wt%, in the figure a: ZSM-5;b:ZSM-5-1%TOS;c:0.1%Au/ZSM-5-1%TOS;d:0.2%Au/ZSM-5-1%TOS;e:0.3%Au/ZSM- 5-1%TOS; f: 0.4%Au/ZSM-5-1%TOS; g: 0.5%Au/ZSM-5-1%TOS.
图3是本发明实施例3中Au/ZSM-5-TOS系列催化剂的正辛烷催化裂化性能评价图（一）；图3用于显示：保持0.1wt%的金负载量，十八烷基三甲氧基硅烷的浓度从1%~4wt%下的正辛烷转化率。Fig. 3 is the n-octane catalytic cracking performance evaluation diagram (1) of Au/ZSM-5-TOS series catalysts in Example 3 of the present invention; The conversion rate of n-octane under the concentration of trimethoxysilane from 1% to 4wt%.
图4是本发明实施例3中Au/ZSM-5-TOS系列催化剂的正辛烷催化裂化性能评价图（二）；图4用于显示：保持0.1wt%的金负载量，十八烷基三甲氧基硅烷的浓度从1%~4wt%下的丙烯选择性。Fig. 4 is the n-octane catalytic cracking performance evaluation diagram (two) of Au/ZSM-5-TOS series catalysts in Example 3 of the present invention; Propylene selectivity under the concentration of trimethoxysilane from 1% to 4wt%.
图5是本发明实施例3中Au/ZSM-5-TOS系列催化剂的正辛烷催化裂化性能评价图（三）；图5用于显示：保持1wt%的十八烷基三甲氧基硅烷的浓度，金纳米粒子的负载量从0.1%~0.5wt%下的正辛烷转化率。Fig. 5 is the n-octane catalytic cracking performance evaluation diagram (three) of Au/ZSM-5-TOS series catalysts in Example 3 of the present invention; Concentration, loading of gold nanoparticles from 0.1% to 0.5wt% n-octane conversion.
图6是本发明实施例3中Au/ZSM-5-TOS系列催化剂的正辛烷催化裂化性能评价图（四）；图6用于显示：保持1wt%的十八烷基三甲氧基硅烷的浓度，金纳米粒子的负载量从0.1%~0.5wt%下的丙烯选择性。Fig. 6 is the n-octane catalytic cracking performance evaluation figure (four) of Au/ZSM-5-TOS series catalyst in the embodiment of the present invention 3; Concentration, propylene selectivity under loading of gold nanoparticles from 0.1% to 0.5wt%.
啶吸附图（二），图中，a: ZSM-5; b: ZSM-5-F; c: ZSM-5-N; d: 0.3%Au/ZSM-5-F；Pyridine adsorption diagram (2), in the figure, a: ZSM-5; b: ZSM-5-F; c: ZSM-5-N; d: 0.3%Au/ZSM-5-F;
图9为本发明实施例5中0.3%Au/ZSM-5-F催化剂的透射电镜图(a)与元素映射图(b)；Fig. 9 is the transmission electron micrograph (a) and the element map (b) of the 0.3%Au/ZSM-5-F catalyst in Example 5 of the present invention;
图10为本发明实施例6条件下Au/ZSM-5-F系列催化剂的正辛烷催化裂化性能评价图（一），图10用于显示正辛烷转化率。Figure 10 is an evaluation chart (1) of n-octane catalytic cracking performance of Au/ZSM-5-F series catalysts under the conditions of Example 6 of the present invention, and Figure 10 is used to show n-octane conversion.
图11为本发明实施例6条件下Au/ZSM-5-F系列催化剂的正辛烷催化裂化性能评价图（二），图11用于显示丙烯选择性。Figure 11 is the n-octane catalytic cracking performance evaluation chart (2) of Au/ZSM-5-F series catalysts under the conditions of Example 6 of the present invention, and Figure 11 is used to show the propylene selectivity.
图12为本发明实施例8中 Au/ZSM-5-F催化剂的稳定性测试结果图。Figure 12 is a diagram of the stability test results of the Au/ZSM-5-F catalyst in Example 8 of the present invention.
图13为本发明实施例9中Au/ZSM-5-F催化剂的透射电镜图。Fig. 13 is a transmission electron microscope image of the Au/ZSM-5-F catalyst in Example 9 of the present invention.
本发明的实施方式Embodiments of the present invention
下面结合具体实施例对本发明做进一步的阐释：Below in conjunction with specific embodiment, the present invention is further explained:
实施例Example 1 Au(en) 2Cl 3 1 Au(en) 2 Cl 3 前驱体的制备Precursor preparation
取2 mL浓度为0.1 g/mL的HAuCl 4溶液，在磁力搅拌的条件下向其中缓慢滴加0.09 mL的乙二胺溶液，继续搅拌30 min后向其中滴加14 mL的无水乙醇，再搅拌30 min。所得悬浊液离心分离，无水乙醇洗涤2遍，所得固体产物在40 ℃下真空干燥12h，得到Au(en) 2Cl 3粉末。 Take 2 mL of HAuCl 4 solution with a concentration of 0.1 g/mL, slowly add 0.09 mL of ethylenediamine solution dropwise to it under the condition of magnetic stirring, continue stirring for 30 min, then add 14 mL of absolute ethanol dropwise to it, and then Stir for 30 min. The resulting suspension was centrifuged, washed twice with absolute ethanol, and the resulting solid product was vacuum-dried at 40°C for 12 hours to obtain Au(en) 2 Cl 3 powder.
实施例Example 2 2 外表面修饰法制备的Prepared by surface modification ZSM-5ZSM-5 载金催化剂gold catalyst
取10 g焙烧后的ZSM-5分子筛于100 mL 0.5~4wt%的十八烷基三甲氧基硅烷的甲苯溶液之中，超声分散均匀，在90 ℃恒温下搅拌6 h，所得悬浮液用无水乙醇洗涤，80 ℃下干燥12 h。然后使用等体积浸渍法负载实施例1制备的0.1~0.5wt%的Au(en) 2Cl 3，浸渍时间不小于24 h，洗涤后干燥至恒重，550 ℃焙烧处理。所得催化剂命名为Au/ZSM-5-TOS。 Take 10 g of calcined ZSM-5 molecular sieve in 100 mL of 0.5~4wt% octadecyltrimethoxysilane toluene solution, ultrasonically disperse evenly, stir at 90 °C for 6 h, and use the obtained suspension Washed with water and ethanol, and dried at 80 °C for 12 h. Then use the equal volume impregnation method to load 0.1~0.5wt% Au(en) 2 Cl 3 prepared in Example 1. The impregnation time is not less than 24 h. After washing, dry to constant weight and roast at 550 °C. The obtained catalyst was named Au/ZSM-5-TOS.
图1和图2为本实施例条件下制备的催化剂的孔经分布图。从图中可以看出改性后的催化剂孔结构更加规整，更有利于择形催化生产丙烯。Figure 1 and Figure 2 are the pore diameter distribution diagrams of the catalyst prepared under the conditions of this example. It can be seen from the figure that the pore structure of the modified catalyst is more regular, which is more conducive to the production of propylene by shape-selective catalysis.
实施例 3 外表面修饰法制备的 ZSM-5 载金催化剂在正辛烷催化裂化增产丙烯中的应用。 Example 3 Application of the ZSM-5 gold-supported catalyst prepared by the external surface modification method in the catalytic cracking of n-octane to increase the production of propylene .
Au/ZSM-5-TOS系列催化剂的评价在定制的催化裂化微反应管中进行。反应温度为260 ~ 460 ℃，将3g催化剂装填于反应管内，当温度到达预设温度后，通过注射器将0.94g正辛烷注入反应器管中，反应70 s。进料完成后，用高纯N 2吹扫，并通过冰水浴分离。气袋收集气相产物，比色管收集液相产物。使用带有OV-101毛细管柱和氢火焰离子化检测器的GC-920(X)色谱分析反应产物。 The evaluation of the Au/ZSM-5-TOS series catalysts was carried out in a custom-made catalytic cracking micro-reaction tube. The reaction temperature was 260-460 °C. 3 g of catalyst was loaded into the reaction tube. When the temperature reached the preset temperature, 0.94 g of n-octane was injected into the reactor tube through a syringe and reacted for 70 s. After the feed was complete, it was purged with high-purity N2 and separated by an ice-water bath. The gas bag collects gas phase products, and the colorimetric tube collects liquid phase products. The reaction products were analyzed by chromatography using a GC-920(X) with an OV-101 capillary column and a hydrogen flame ionization detector.
图3至图6为本实施例条件下Au/ZSM-5-TOS系列催化剂的正辛烷催化裂化性能评价。从图中可以看出，0.2%Au/ZSM-5-1%TOS催化剂在实现正辛烷完全转化的同时，使得反应温度降低100℃以上。Figure 3 to Figure 6 are the n-octane catalytic cracking performance evaluation of Au/ZSM-5-TOS series catalysts under the conditions of this example. It can be seen from the figure that the 0.2%Au/ZSM-5-1%TOS catalyst reduces the reaction temperature by more than 100°C while realizing the complete conversion of n-octane.
实施例Example 4 4 外表面修饰法制备的Prepared by surface modification ZSM-5ZSM-5 载金催化剂在轻柴油催化裂化增产丙烯中的应用Application of supported gold catalyst in catalytic cracking of light oil to increase propylene production
0.2%Au/ZSM-5-1%TOS系列催化剂的评价在定制的催化裂化微反应管中进行。反应温度为260 ~ 460 ℃，将3g催化剂装填于反应管内，当温度到达预设温度后，通过注射器将0.94g轻柴油注入反应器管中，反应70s。进料完成后，用高纯N 2吹扫，并通过冰水浴分离。气袋收集气相产物，比色管收集液相产物。使用带有OV-101毛细管柱和氢火焰离子化检测器的GC-920(X)色谱分析反应产物。 The evaluation of 0.2%Au/ZSM-5-1%TOS series catalysts was carried out in a custom-made catalytic cracking micro-reaction tube. The reaction temperature is 260 ~ 460 ℃, 3g of catalyst is packed in the reaction tube, when the temperature reaches the preset temperature, 0.94g of light diesel oil is injected into the reactor tube through the syringe, and reacted for 70s. After the feed was complete, it was purged with high-purity N2 and separated by an ice-water bath. The gas bag collects gas phase products, and the colorimetric tube collects liquid phase products. The reaction products were analyzed by chromatography using a GC-920(X) with an OV-101 capillary column and a hydrogen flame ionization detector.
表1为本实施例条件下催化剂的轻柴油催化裂化性能评价表。从表中可以发现，改性后催化剂的轻柴油转化率和丙烯选择性均表现出一定优势。Table 1 is an evaluation table of the light diesel oil catalytic cracking performance of the catalyst under the conditions of this example. It can be seen from the table that the conversion of light oil and the selectivity of propylene of the modified catalyst both show certain advantages.
表1 改性后催化剂的轻柴油催化裂化性能评价表Table 1 Evaluation table of light diesel oil catalytic cracking performance of modified catalyst
 
实施例Example 5 5 脱铝法制备的prepared by dealumination ZSM-5ZSM-5 载金催化剂gold catalyst
取10g焙烧后的ZSM-5分子筛置于200 ml醋酸铵（3 mol/L）缓冲溶液中，搅拌均匀，在80℃下滴加一定量的六氟硅酸铵溶液（六氟硅酸铵与分子筛中Al的摩尔比为1:1），继续搅拌3 h。待溶液冷却至室温，离心洗涤，干燥至恒重后焙烧得ZSM-5-F催化剂（对照组催化剂未添加缓冲溶剂命名为ZSM-5-N），然后使用等体积浸渍法负载不同浓度的Au(en) 2Cl 3，浸渍时间不小于24 h，洗涤后干燥至恒重, 550 ℃焙烧处理。 Take 10 g of roasted ZSM-5 molecular sieve and place it in 200 ml of ammonium acetate (3 mol/L) buffer solution, stir evenly, and add a certain amount of ammonium hexafluorosilicate solution (ammonium hexafluorosilicate and The molar ratio of Al in the molecular sieve was 1:1), and the stirring was continued for 3 h. After the solution was cooled to room temperature, it was washed by centrifugation, dried to constant weight and then calcined to obtain ZSM-5-F catalyst (the catalyst of the control group was named ZSM-5-N without adding buffer solvent), and then loaded with different concentrations of Au by equal volume impregnation method (en) 2 Cl 3 , the immersion time is not less than 24 h, washed and dried to constant weight, and roasted at 550 ℃.
图7和图8为本实施例条件下制备的催化剂的吡啶吸附图。从图中可以看出改性后的催化剂B酸含量及强度增加，而B酸的增强有助于裂解反应的发生。图9为本实施例条件下制备的催化剂的透射电镜图（a）与元素映射图(b)。从图中可以看出较少的Au纳米粒子沉积在分子筛表面，而元素映射的结果反映出未观察到的小尺寸金有可能进入分析筛孔道之中，从孔径分布图也可以推测得到这一结果。Figure 7 and Figure 8 are the pyridine adsorption diagrams of the catalyst prepared under the conditions of this example. It can be seen from the figure that the B acid content and strength of the modified catalyst increase, and the enhancement of B acid helps the cracking reaction to occur. Fig. 9 is a transmission electron microscope image (a) and an elemental map (b) of the catalyst prepared under the conditions of this example. It can be seen from the figure that fewer Au nanoparticles are deposited on the surface of the molecular sieve, and the results of elemental mapping reflect that the unobserved small-sized gold may enter the pores of the analytical sieve, which can also be inferred from the pore size distribution figure. result.
实施例Example 6 6 脱铝法制备的prepared by dealumination ZSM-5ZSM-5 载金催化剂在正辛烷催化裂化增产丙烯中的应用Application of Gold-supported Catalyst in Catalytic Cracking of n-Octane to Increase Production of Propylene
Au/ZSM-5-F催化剂的评价在定制的催化裂化微反应管中进行。反应温度为260 ~ 460 ℃，3g催化剂装填于反应管内，当温度到达预设温度后，通过注射器将0.94 g正辛烷注入反应器管中，反应70 s。进料完成后，用高纯N 2吹扫，并通过冰水浴分离。气袋收集气相产物，比色管收集液相产物。使用带有OV-101毛细管柱和氢火焰离子化检测器的GC-920(X)色谱分析反应产物。 Evaluation of the Au/ZSM-5-F catalyst was carried out in a custom-made FCC microreactor. The reaction temperature was 260-460 °C, and 3 g of catalyst was packed in the reaction tube. When the temperature reached the preset temperature, 0.94 g of n-octane was injected into the reactor tube through a syringe and reacted for 70 s. After the feed was complete, it was purged with high-purity N2 and separated by an ice-water bath. The gas bag collects gas phase products, and the colorimetric tube collects liquid phase products. The reaction products were analyzed by chromatography using a GC-920(X) with an OV-101 capillary column and a hydrogen flame ionization detector.
图10和图11为本实施例条件下Au/ZSM-5-F系列催化剂的正辛烷催化裂化性能评价图。从图中可以看出，0.3%Au/ZSM-5-F催化剂在实现正辛烷完全转化的同时，使得反应温度降低150℃以上。Figure 10 and Figure 11 are evaluation diagrams of n-octane catalytic cracking performance of Au/ZSM-5-F series catalysts under the conditions of this example. It can be seen from the figure that the 0.3%Au/ZSM-5-F catalyst reduces the reaction temperature by more than 150°C while realizing the complete conversion of n-octane.
实施例Example 7 7 脱铝法制备的prepared by dealumination ZSM-5ZSM-5 载金催化剂在轻柴油催化裂化增产丙烯中的应用Application of supported gold catalyst in catalytic cracking of light oil to increase propylene production
Au/ZSM-5-F催化剂的评价在定制的催化裂化微反应管中进行。反应温度为260 ~ 460 ℃，3g催化剂装填于反应管内，当温度到达预设温度后，通过注射器将0.94 g轻柴油注入反应器管中，反应70 s。进料完成后，用高纯N 2吹扫，并通过冰水浴分离。气袋收集气相产物，比色管收集液相产物。使用带有OV-101毛细管柱和氢火焰离子化检测器的GC-920(X)色谱分析反应产物。 Evaluation of the Au/ZSM-5-F catalyst was carried out in a custom-made FCC microreactor. The reaction temperature was 260-460 °C, and 3 g of catalyst was packed in the reaction tube. When the temperature reached the preset temperature, 0.94 g of light diesel oil was injected into the reactor tube through a syringe and reacted for 70 s. After the feed was complete, it was purged with high-purity N2 and separated by an ice-water bath. The gas bag collects gas phase products, and the colorimetric tube collects liquid phase products. The reaction products were analyzed by chromatography using a GC-920(X) with an OV-101 capillary column and a hydrogen flame ionization detector.
表2为实施例条件下催化剂的轻柴油催化裂化性能评价表。从表中可以发现，改性后催化剂的轻柴油转化率和丙烯选择性均表现出一定优势。Table 2 is an evaluation table of the light diesel oil catalytic cracking performance of the catalyst under the conditions of the examples. It can be seen from the table that the conversion of light oil and the selectivity of propylene of the modified catalyst both show certain advantages.
表2 改性后催化剂的轻柴油催化裂化性能评价表Table 2 Evaluation table of light diesel oil catalytic cracking performance of modified catalyst
实施例Example 8 8 脱铝法制备的prepared by dealumination ZSM-5ZSM-5 载金催化剂在正辛烷催化裂化增产丙烯中稳定性的测试Stability test of gold-supported catalyst in n-octane catalytic cracking to increase propylene production
Au/ZSM-5-F催化剂的稳定性测试在定制的催化裂化微反应管中进行。反应温度为360 ℃，3g催化剂装填于反应管内，当温度到达360℃后，通过注射器将0.94 g正辛烷注入反应器管中，反应70 s。进料完成后，用高纯N 2吹扫，并通过冰水浴分离。气袋收集气相产物，比色管收集液相产物。重复进样测试，循环15次。使用带有OV-101毛细管柱和氢火焰离子化检测器的GC-920(X)色谱分析反应产物。 Stability testing of the Au/ZSM-5-F catalyst was carried out in a custom-made FCC micro-reaction tube. The reaction temperature was 360 °C, and 3 g of catalyst was packed in the reaction tube. When the temperature reached 360 °C, 0.94 g of n-octane was injected into the reactor tube through a syringe and reacted for 70 s. After the feed was complete, it was purged with high-purity N2 and separated by an ice-water bath. The gas bag collects gas phase products, and the colorimetric tube collects liquid phase products. Repeat the injection test and cycle 15 times. The reaction products were analyzed by chromatography using a GC-920(X) with an OV-101 capillary column and a hydrogen flame ionization detector.
图12为Au/ZSM-5-F催化剂的稳定性测试结果图。从图中可以看出改性后催化剂正辛烷转化率和丙烯产量均在一定范围内波动，15次循环后均无明显下降。Figure 12 is a diagram of the stability test results of the Au/ZSM-5-F catalyst. It can be seen from the figure that the n-octane conversion rate and propylene output of the modified catalyst fluctuate within a certain range, and there is no obvious decrease after 15 cycles.
实施例Example 9 9 金溶胶法制备的prepared by the gold sol method ZSM-5ZSM-5 载金催化剂gold catalyst
取一定量的 HAuCl 4溶液，加入适量去离子水，加热至剧烈沸腾。快速加入一定量的柠檬酸钠溶液，柠檬酸钠与HAuCl 4的摩尔比为5，等到溶液变为酒红色后继续煮沸20min时间,自然冷却至室温。加入上述ZSM-5-F催化剂搅拌吸附24h后洗涤干燥，理论载金量为0.5wt%。 Take a certain amount of HAuCl 4 solution, add an appropriate amount of deionized water, and heat to vigorous boiling. Quickly add a certain amount of sodium citrate solution, the molar ratio of sodium citrate to HAuCl4 is 5, wait until the solution turns wine red, continue to boil for 20min, and cool down to room temperature naturally. Add the above-mentioned ZSM-5-F catalyst, stir and adsorb for 24 hours, then wash and dry, and the theoretical gold loading is 0.5wt%.
图13为Au/ZSM-5-F催化剂的透射电镜图，从图中可以看出金溶胶法可以更好的控制金纳米粒子的尺寸，使得金纳米粒子分散更加均匀。Figure 13 is a transmission electron microscope image of the Au/ZSM-5-F catalyst. It can be seen from the figure that the gold sol method can better control the size of gold nanoparticles and make the dispersion of gold nanoparticles more uniform.
本发明可采用沉积沉淀法制备Au/ZSM-5催化剂，沉积沉淀法需控制PH值为9~10，或采用浸渍法将金纳米粒子负载在ZSM-5分子筛上，需浸渍24 h以上，或采用金溶胶吸附法，吸附时间控制在24 h以上。所述催化剂的理论载金量质量百分比为0.1%~0.5%。In the present invention, the Au/ZSM-5 catalyst can be prepared by a deposition-precipitation method, and the pH value of the deposition-precipitation method needs to be controlled to be 9-10, or the gold nanoparticles are loaded on the ZSM-5 molecular sieve by the impregnation method, which needs to be impregnated for more than 24 h, or The gold sol adsorption method was adopted, and the adsorption time was controlled above 24 h. The theoretical gold loading mass percentage of the catalyst is 0.1%-0.5%.

Claims (10)

  1. 修饰ZSM-5载金催化剂的制备方法，其特征在于包括ZSM-5修饰和纳米金负载步骤：The preparation method of modified ZSM-5 loaded gold catalyst is characterized in that comprising ZSM-5 modified and nano-gold loaded steps:
    （一）ZSM-5修饰方法(1) ZSM-5 modification method
    （1）外表面修饰法处理ZSM-5分子筛母体，包括以下步骤：取焙烧后的ZSM-5分子筛于修饰剂溶液之中，超声分散均匀，恒温搅拌，所得悬浮液用无水乙醇洗涤，干燥至恒重；或者，(1) The ZSM-5 molecular sieve matrix is treated by the external surface modification method, including the following steps: take the roasted ZSM-5 molecular sieve in the modifier solution, ultrasonically disperse it evenly, stir at a constant temperature, wash the obtained suspension with absolute ethanol, and dry to constant weight; or,
    （2）六氟硅酸铵处理ZSM-5分子筛母体，包括以下步骤：取焙烧后的ZSM-5分子筛置于醋酸铵缓冲溶液中，搅拌，加入六氟硅酸铵溶液，继续搅拌，冷却，离心洗涤，干燥至恒重后焙烧；(2) Treating the ZSM-5 molecular sieve matrix with ammonium hexafluorosilicate includes the following steps: take the roasted ZSM-5 molecular sieve and place it in an ammonium acetate buffer solution, stir, add ammonium hexafluorosilicate solution, continue to stir, cool, Centrifugal washing, drying to constant weight and roasting;
    （二）经过步骤（一）修饰的ZSM-5负载纳米金得到催化剂；所述催化剂的理论载金量为0.1~0.5 wt%。(2) A catalyst is obtained by loading nano-gold on ZSM-5 modified in step (1); the theoretical gold loading of the catalyst is 0.1-0.5 wt%.
  2. 如权利要求1所述的修饰ZSM-5载金催化剂的制备方法，其特征在于：所述步骤（二）采用金溶胶吸附法，将修饰后的ZSM-5分子筛加入到金溶胶中，搅拌吸附。The preparation method of modified ZSM-5 gold-loaded catalyst according to claim 1, characterized in that: said step (2) adopts the gold sol adsorption method, adding the modified ZSM-5 molecular sieve into the gold sol, stirring and adsorbing .
  3. 如权利要求2所述的修饰ZSM-5载金催化剂的制备方法，其特征在于所述金溶胶的制备方法为：将HAuCl 4溶液加热至沸腾；然后加入柠檬酸钠溶液，等到溶液变为酒红色后继续煮沸，冷却。 The preparation method of modified ZSM-5 loaded gold catalyst as claimed in claim 2, is characterized in that the preparation method of described gold sol is: HAuCl solution is heated to boiling; Then add sodium citrate solution, wait until solution becomes wine After turning red, continue to boil and cool.
  4. 如权利要求3所述的修饰ZSM-5载金催化剂的制备方法，其特征在于：所述柠檬酸钠与HAuCl 4的摩尔比为2~10；所述的煮沸时长为20~50 min。 The preparation method of the modified ZSM-5 gold-loaded catalyst according to claim 3, characterized in that: the molar ratio of the sodium citrate to HAuCl is 2-10; the boiling time is 20-50 min.
  5. 如权利要求1所述的修饰ZSM-5载金催化剂的制备方法，其特征在于：所述步骤（二）以Au(en) 2Cl 3作为金前驱体；所述（Au(en) 2Cl 3）的制备方法为：搅拌下向HAuCl 4溶液中加入乙二胺溶液，继续搅拌均匀后滴加无水乙醇，再继续搅拌，所得悬浊液离心分离，无水乙醇洗涤，干燥得到Au(en) 2Cl 3。 The preparation method of modified ZSM-5 supported gold catalyst according to claim 1, characterized in that: said step (two) uses Au(en) 2 Cl 3 as a gold precursor; said (Au(en) 2 Cl 3 ) The preparation method is as follows: add ethylenediamine solution to the HAuCl 4 solution under stirring, continue to stir evenly, add absolute ethanol dropwise, continue stirring, centrifuge the obtained suspension, wash with absolute ethanol, and dry to obtain Au( en) 2 Cl 3 .
  6. 如权利要求5所述的修饰ZSM-5载金催化剂的制备方法，其特征在于：所述HAuCl 4与乙二胺的质量比为10~30；所述无水乙醇与HAuCl 4的质量比为10~20。 The preparation method of modified ZSM-5 gold-loaded catalyst as claimed in claim 5, is characterized in that: described HAuCl The mass ratio with ethylenediamine is 10～30; Described dehydrated alcohol and HAuCl The mass ratio is 10~20.
  7. 如权利要求1所述的修饰ZSM-5载金催化剂的制备方法，其特征在于：所述步骤（二）以HAuCl 4溶液作为金前驱体。 The method for preparing a modified ZSM-5 gold-supported catalyst according to claim 1, characterized in that: the step (2) uses HAuCl 4 solution as a gold precursor.
  8. 如权利要求1至7任意一项所述的修饰ZSM-5载金催化剂的制备方法，其特征在于所述的修饰剂为包括十八烷基三甲氧基硅烷和十二烷基三甲氧基硅烷在内的分子尺寸大于孔径的修饰剂；所述ZSM-5与修饰剂的质量比为0.5~20；所述修饰剂的质量浓度为0.01~0.2。The preparation method of modified ZSM-5 supported gold catalyst as described in any one of claims 1 to 7, is characterized in that described modifying agent comprises octadecyltrimethoxysilane and dodecyltrimethoxysilane A modifier whose molecular size is larger than the pore diameter; the mass ratio of the ZSM-5 to the modifier is 0.5-20; the mass concentration of the modifier is 0.01-0.2.
  9. 如权利要求1至7任意一项所述的修饰ZSM-5载金催化剂的制备方法，其特征在于所述的六氟硅酸铵与ZSM-5分子筛中Al的摩尔比为0.5~2；所述的醋酸铵与六氟硅酸铵的摩尔比为100~200。The preparation method of modified ZSM-5 gold-loaded catalyst as described in any one of claims 1 to 7, it is characterized in that the mol ratio of Al in described ammonium hexafluorosilicate and ZSM-5 molecular sieve is 0.5～2; The molar ratio of ammonium acetate to ammonium hexafluorosilicate is 100-200.
  10. 所述修饰ZSM-5载金催化剂用于正辛烷催化裂化制备丙烯或者轻柴油催化裂化制备丙烯。The modified ZSM-5 gold-carrying catalyst is used for preparing propylene by catalytic cracking of n-octane or catalytic cracking of light oil to prepare propylene.
PCT/CN2022/083641 2022-01-30 2022-03-29 Preparation method for modified zsm-5 gold-loaded catalyst and use thereof WO2023142258A1 (en)

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