WO2022148416A1 - Zsm-23分子筛及其制备方法 - Google Patents

Zsm-23分子筛及其制备方法 Download PDF

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WO2022148416A1
WO2022148416A1 PCT/CN2022/070636 CN2022070636W WO2022148416A1 WO 2022148416 A1 WO2022148416 A1 WO 2022148416A1 CN 2022070636 W CN2022070636 W CN 2022070636W WO 2022148416 A1 WO2022148416 A1 WO 2022148416A1
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molecular sieve
zsm
silicon
hours
sio
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PCT/CN2022/070636
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English (en)
French (fr)
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陈玉晶
樊宏飞
于政敏
孙晓艳
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中国石油化工股份有限公司
中石化（大连）石油化工研究院有限公司
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Priority to US18/260,640 priority Critical patent/US20240059574A1/en
Priority to EP22736578.0A priority patent/EP4276068A1/en
Priority to JP2023541303A priority patent/JP2024503645A/ja
Priority to KR1020237026808A priority patent/KR20230126223A/ko
Priority to CA3207628A priority patent/CA3207628A1/en
Publication of WO2022148416A1 publication Critical patent/WO2022148416A1/zh

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Definitions

  • the invention relates to a ZSM-23 molecular sieve, a preparation method and application thereof, and in particular to a ZSM-23 molecular sieve with low strong acid content, a preparation method and application thereof.
  • ZSM-23 molecular sieve is a molecular sieve material with high silicon-aluminum ratio, with MTT topology, and its one-dimensional teardrop-shaped channel is composed of ten-membered rings. With its unique pore structure and tunable acid properties, ZSM-23 molecular sieves are widely used in the fields of separation, adsorption and catalysis, and play an irreplaceable role. Especially in the petrochemical industry, it has a good performance in long-chain alkane and olefin hydrocracking, alkane and aromatic hydrocarbon isomerization, etc. Therefore, it is of great significance to prepare ZSM-23 molecular sieve with excellent performance.
  • US4076842 firstly disclosed a method for synthesizing ZSM-23 molecular sieve by using pyrrolidine as a template agent. After that, US4490342 and US5707601 successively disclosed the conditions for synthesizing ZSM-23 molecular sieve in the system of diquat-7 or small molecular amine and neutral amine as template agent.
  • CN101214971 discloses a synthesis method of nano ZSM-23 molecular sieve.
  • Patent CN101613114 discloses a method for synthesizing ZSM-23 molecular sieve with ZSM-22 or ZSM-23 molecular sieve as crystal seed, supplemented by a small amount of ethylamine, n-butylamine and other template agents.
  • CN102897785 adopts step-by-step treatment.
  • organic template agent or aqueous solution is mixed with aluminum source, and treated in a closed reaction vessel at 50-190 ° C for a period of time; After hydrothermal crystallization, HZSM-23 molecular sieve was obtained.
  • CN102992346 also discloses a method for synthesizing ZSM-23 molecular sieve without a template agent. After mixing water with an aluminum source, adding a sodium source and a silicon source, stirring evenly, adding seed crystals for hydrothermal crystallization to obtain the original powder of ZSM-23 molecular sieve.
  • the present invention provides a ZSM-23 molecular sieve and a preparation method and application thereof.
  • the ZSM-23 molecular sieve has low strong acid content and the ZSM-23 molecular sieve has a simple preparation method.
  • the invention relates to a ZSM-23 molecular sieve, wherein the total acid content of the ZSM-23 molecular sieve is 0.05-0.25 mmol/g, preferably 0.06-0.22 mmol/g, more preferably 0.06-0.20 mmol/g;
  • the strong acid content of the ZSM-23 molecular sieve accounts for 5-33% of the total acid content, preferably 7-33%, more preferably 9-33%, or further preferably 7-31%.
  • the strong acid refers to an acid whose corresponding desorption temperature is above 350°C in temperature-programmed desorption by NH 3 (NH 3 -TPD), wherein optionally the ZSM -23 molecular sieves are calcined or uncalcined.
  • the ZSM-23 molecular sieve described in the present invention may refer to the product obtained by drying after crystallization in the process of preparing the molecular sieve (that is, not calcined), or it may refer to the product obtained by drying in the process of preparing the molecular sieve. After crystallization, the resulting product is dried and calcined (ie, calcined).
  • the crystal grain size of the ZSM-23 molecular sieve is 100-700 nm, preferably the crystal grain size is 200-600 nm, and more preferably the crystal grain size is 300-500 nm.
  • the ZSM-23 molecular sieves have a SiO 2 /Al 2 O 3 molar ratio of 40-300, a specific surface area of 200-400 m 2 /g, and a pore volume of 0.25-0.50 cm 3 /g; preferably , the SiO 2 /Al 2 O 3 molar ratio of the ZSM-23 molecular sieve is 40-200 or 50-200, the specific surface area is 280-370 m 2 /g, and the pore volume is 0.28-0.40 cm 3 /g.
  • the relative crystallinity of the ZSM-23 molecular sieve is 95-130%, and the relative crystallinity is 93-120% after 600 ° C steam hydrothermal treatment for 2 hours; preferably the relative crystallinity is 98-120% , the relative crystallinity is 95-115% after 600 °C steam water heat treatment for 2 hours.
  • a kind of preparation method of ZSM-23 molecular sieve of the present invention comprises the following content:
  • step (2) adding alkali source and silicon source to the mixed solution of step (1);
  • ZSM is obtained after the material obtained in step (2) is subjected to crystallization (eg static crystallization - crystallization without stirring), optional filtration and washing, drying, and optional calcination -23 molecular sieve.
  • the template agent is one or more of isopropylamine, pyrrolidine, N,N-dimethylformamide, and dimethylamine.
  • the amorphous silica-alumina and/or amorphous silica-alumino precursors are based on an alkaline aluminum source (for example, an aluminate or a meta-aluminate, such as sodium aluminate, potassium aluminate, meta-aluminum sodium, potassium metaaluminate, etc.); in other words, the amorphous silica-alumina and/or amorphous silica-alumina precursors do not include strong acid radicals, such as sulfate radicals, nitrate radicals, and the like.
  • an alkaline aluminum source for example, an aluminate or a meta-aluminate, such as sodium aluminate, potassium aluminate, meta-aluminum sodium, potassium metaaluminate, etc.
  • the amorphous silica-alumina and/or amorphous silica-alumina precursors do not include strong acid radicals, such as sulfate
  • the molar ratio of silicon (calculated as silicon oxide):aluminum (calculated as alumina) in the mixed solution is 1:(0.10-0.85), preferably 1:(0.20-0.79), and further It is preferably 1:(0.24-0.78);
  • the molar ratio of the aluminum (calculated as alumina):template is 1:(10-100), preferably 1:(15-85), more preferably 1:(20 -65).
  • an amorphous silicon-aluminum precursor is prepared by a carbonization method, and then a template agent is added to the amorphous silicon-aluminum precursor to obtain the mixed solution.
  • the specific preparation process of a non-limiting amorphous silica-alumina precursor in the embodiment of the present invention is as follows: respectively preparing an aluminum source (that is, an alkaline aluminum source, for example, an aluminate such as sodium aluminate, potassium aluminate, etc., preferably Sodium aluminate) solution and silicon-containing compound solution; mix the aluminum source solution with a part of the silicon-containing compound solution, and introduce CO 2 gas to form a gel.
  • an aluminum source that is, an alkaline aluminum source, for example, an aluminate such as sodium aluminate, potassium aluminate, etc., preferably Sodium aluminate
  • the volume of the introduced CO 2 gas accounts for 50- of the total volume introduced When it is 100%, preferably 70-90%, the remaining part of the silicon-containing compound solution is added, and then the remaining CO 2 gas is introduced, optionally after aging to obtain an amorphous silicon-alumina precursor.
  • the remaining part of the silicon-containing compound solution is 5-85 wt %, preferably 30-70 wt %, calculated as silicon dioxide, of the total amount of silicon-containing compound solution added to the silicon-containing compound solution.
  • the reaction temperature of the gel formation is 10-40° C., preferably 15-35° C., and the pH value after the gel formation is controlled to be 9-12.
  • the silicon-containing compound solution is water glass and/or sodium silicate solution.
  • the concentration of the aluminum source solution is 15-60 gAl 2 O 3 /L in terms of Al 2 O 3 mass, and in terms of SiO 2 mass, the concentration of the silicon-containing compound solution is is 40-260 gSiO 2 /L, and the concentration of the CO 2 gas is 30-60 v%.
  • the aging time is 5-60 minutes, preferably 10-30 minutes; the aging temperature is 10-40°C, preferably 15-35°C.
  • the mixed solution is stirred at 10-35°C for 0.2-1.5 hours, preferably at 10-25°C for 0.5-1 hour.
  • SiO 2 : Al 2 O 3 : R 2 O (alkali source, wherein R is an alkali metal, such as sodium, potassium): H 2 O 1: (0.0025-0.025): (0.015-0.08): (30-80)
  • the silicon source is one or more of fumed silica, silica sol and water glass
  • the alkali source is a kind of sodium hydroxide, potassium hydroxide and ammonia water or several.
  • the crystallization conditions are: 150-200°C for 8-72 hours, preferably 160-180°C for 10-48 hours; the drying temperature is 60-130°C, and the time is 2 -12 hours, preferably 80-120 °C drying for 4-8 hours; calcination temperature is 500-600 °C, time is 2-8 hours, preferably 530-570 °C calcination for 3-6 hours or 4-6 hours.
  • a ZSM-23 molecular sieve is characterized in that: the total acid amount of described ZSM-23 molecular sieve is 0.05-0.25mmol/g, preferably, 0.06-0.22mmol/g, more preferably, 0.06-0.20mmol/g g; the strong acid content of the ZSM-23 molecular sieve accounts for 5-33% of the total acid content, preferably, 7-33%, more preferably, 9-33%, or further preferably, 7-31%, further more Preferably, 10-28%; wherein the strong acid refers to an acid whose corresponding desorption temperature is above 350°C in the temperature-programmed desorption of NH 3 (NH 3 -TPD), wherein optionally the ZSM-23 Molecular sieves are dried and calcined samples.
  • the molecular sieve according to any one of the preceding schemes characterized in that: the ZSM-23 molecular sieve is about 11.3°+/-0.3° (eg, +/-0.2° or +/-0.3° in XRD spectrum) There are characteristic diffraction peaks at 0.1°).
  • the molecular sieve according to any one of the preceding schemes characterized in that: the ZSM-23 molecular sieve is 11.2-11.5°, 19.5-19.9°, 20.7-21.0°, 22.8-23.1° in XRD spectrum 2 ⁇ There are characteristic diffraction peaks.
  • the grain size of the ZSM-23 molecular sieve is 100-700 nm, preferably the grain size is 200-600 nm, and further preferably the grain size is 300-700 nm. 500nm.
  • the ZSM-23 molecular sieve has a SiO 2 /Al 2 O 3 molar ratio of 35-300, a specific surface area of 200-400 m 2 /g, and a pore volume of 200-400 m 2 /g. is 0.25-0.50cm 3 /g; preferably, the ZSM-23 molecular sieve SiO 2 /Al 2 O 3 molar ratio is 38-200, the specific surface area is 280-370m 2 /g, and the pore volume is 0.28-0.40cm 3 /g.
  • the relative crystallinity of the ZSM-23 molecular sieve after calcination is 95-130%, and the relative crystallinity is 93 after 600 ° C steam hydrothermal treatment for 2 hours. -120%; preferably, the relative crystallinity after calcination is 98-120%, and the relative crystallinity is 95-115% after 600°C steam hydrothermal treatment for 2 hours.
  • Formulating a mixed solution containing a template agent, and amorphous silica-alumina and/or amorphous silica-alumina precursors are based on an alkaline aluminum source (such as , aluminate or meta-aluminate, such as sodium aluminate, potassium aluminate, sodium meta-aluminate, potassium meta-aluminate, etc.);
  • an alkaline aluminum source such as , aluminate or meta-aluminate, such as sodium aluminate, potassium aluminate, sodium meta-aluminate, potassium meta-aluminate, etc.
  • step (2) adding alkali source and silicon source to the mixed solution of step (1);
  • ZSM-23 molecular sieve is obtained after the material obtained in step (2) is crystallized, optionally filtered and washed, dried, and optionally calcined.
  • step (1) described templating agent is in isopropylamine, pyrrolidine, N,N-dimethylformamide and dimethylamine. one or more of them.
  • step (1) the molar ratio of silicon (calculated as silicon oxide):aluminum (calculated as alumina) in the mixed solution is 1:( 0.10-0.85), preferably 1: (0.20-0.79), more preferably 1: (0.24-0.78); the molar ratio of the aluminum (calculated as alumina): the template agent is 1: (10-100), Preferably it is 1:(15-85), More preferably, it is 1:(20-65).
  • step (1) a carbonization method is used to prepare an amorphous silicon-aluminum precursor, and then a templating agent is added to the amorphous silicon-aluminum precursor to obtain the mixed solution.
  • the preparation process of the amorphous silicon-alumina precursor in the step (1) is as follows: respectively prepare an aluminum source (for example, aluminate, preferably sodium aluminate) ) solution and a silicon-containing compound solution; mix the aluminum source solution with a part of the silicon-containing compound solution, and introduce CO 2 gas to form a gel.
  • an aluminum source for example, aluminate, preferably sodium aluminate
  • CO 2 gas to form a gel.
  • the remaining part of the silicon-containing compound solution, calculated as silicon dioxide accounts for 5-85 wt% of the total amount of silicon-containing compound solution added to the silicon-containing compound solution, calculated as silicon dioxide, It is preferably 30-70 wt%.
  • reaction temperature of the gel formation is 10-40°C, preferably 15-35°C, and the pH value after the gel formation is controlled is 9-12 .
  • silicon-containing compound solution is water glass and/or sodium silicate solution.
  • the aging time is 5-60 minutes, preferably 10-30 minutes; and the aging temperature is 10-40°C, preferably 15-35°C.
  • step (1) the mixed solution is stirred at 10-35°C for 0.2-1.5 hours, preferably at 10-25°C for 0.5-1 hour.
  • an alkali source is added and a silicon source is supplemented.
  • step (2) the silicon source is one or more of fumed silica, silica sol and water glass, and the alkali The source is one or more of sodium hydroxide, potassium hydroxide, and ammonia water.
  • step (3) the crystallization conditions are: 150-200°C for 8-72 hours, preferably 160-180°C for crystallization 10-48 hours; drying temperature is 60-130°C, time is 2-12 hours, preferably 80-120°C for 4-8 hours; roasting temperature is 500-600°C, time is 2-8 hours, preferably 530- Bake at 570°C for 3-6 hours or 4-6 hours.
  • the present invention has the following advantages:
  • the template agent in the preparation process of the amorphous silica-alumina precursor, all the aluminum sources required for the synthesis are added, which promotes the generation of the primary structural unit of the molecular sieve;
  • the template agent when the template agent is added to the medium, the template agent will preferentially chelate with the Al species, and then adsorb on the surface of the formed primary structural unit to realize the pre-assembly of the molecular sieve structure and generate a large number of crystal nuclei; at the same time, it can better control the binding site of Al atoms , which is helpful to obtain ZSM-23 with more weak acid sites and medium strong acid sites after crystallization.
  • the method of the invention expands the synthetic silicon-aluminum ratio range of ZSM-23, shortens the crystallization time of the molecular sieve, reduces the amount of template agent in the synthesis process of the ZSM-23 molecular sieve, and the obtained molecular sieve product has excellent performance and is a green and feasible product. industrial production route.
  • the ZSM-23 molecular sieve sample synthesized by the method of the invention has high crystallinity, small grain size, more weak acids and medium and strong acids, low content of strong acids, good thermal stability and hydrothermal stability, and can be used as a kind of Excellent adsorbent or catalytic material.
  • Fig. 1 is the XRD spectrogram of the synthetic product of the present invention.
  • Fig. 2 is the scanning electron microscope picture of the synthetic product of the present invention.
  • the specific surface area and pore volume were determined by a low-temperature liquid nitrogen physical adsorption method using an ASAP 2405 physical adsorption instrument from Micromeritics, USA.
  • the molar ratio of silicon to aluminum was determined by chemical analysis.
  • the XRD patterns of the samples were collected using a Dmax2500 X-ray diffractometer produced by Rigaku Corporation.
  • the relative crystallinity of the molecular sieve is determined by X-ray powder diffraction (XRD), specifically, the sum of the heights of the diffraction peaks at 2 ⁇ of about 11.3 and 19.5-23° in the XRD spectrum of the conventional ZSM-23 molecular sieve is taken as the crystallinity 100%, other The samples were compared to obtain relative crystallinity.
  • the ZSM-23 molecular sieve has characteristic diffraction peaks at about 11.3° +/- 0.3° (eg +/- 0.2° or +/- 0.1°) at 2 ⁇ in the XRD spectrum.
  • ZSM-23 molecular sieve has characteristic diffraction peaks at 2 ⁇ of 11.2-11.5°, 19.5-19.9°, 20.7-21.0°, and 22.8-23.1° in the XRD spectrum.
  • the grain size was obtained by JSM-7500F field emission scanning electron microscope from JEOL, Japan.
  • the acid distribution (including total acid content and strong acid content) was measured by NH 3 temperature programmed desorption (NH 3 -TPD), wherein the acid content corresponding to the desorption temperature above 350°C was regarded as the strong acid content.
  • the amount of acid is calculated as H + .
  • wt% is mass fraction
  • v% is volume fraction
  • a working solution of sodium aluminate with a concentration of 40 g Al 2 O 3 /L was prepared, and a sodium silicate solution containing 28 wt % of SiO 2 was taken, and then diluted to a working solution of 100 g SiO 2 /L of sodium silicate. Take 150mL of sodium aluminate working solution and put it in the gel-forming tank, then add 50mL of sodium silicate working solution, control the reaction temperature to 20°C, and pass CO2 gas with a concentration of 50v%.
  • IPA/ SiO2 0.7 (IPA is the template isopropylamine), to the above-obtained Add isopropylamine to the amorphous silica-alumina precursor, and stir at 15°C for 0.8 hours to obtain a mixed solution containing the amorphous silica-alumina precursor and the template; then, add a mixture of sodium hydroxide, silica sol and water to it. The mixture was stirred uniformly to obtain a silica-alumina gel.
  • the gel obtained above was poured into a stainless steel reactor, and statically crystallized at 160° C. for 20 hours. After crystallization, after filtering and washing to neutrality, drying at 120 ° C to obtain molecular sieve product ZSM-23-1; after calcining in air at 550 ° C for 3 hours, the relative crystallinity after calcination was measured; after 600 After 2 hours of water vapor hydrothermal treatment, the hydrothermal stability was measured, and the specific properties are shown in Table 1.
  • Fig. 1 is the XRD spectrum of the molecular sieve
  • Fig. 2 is the scanning electron microscope picture of the molecular sieve, which confirms that the obtained molecular sieve is a ZSM-23 molecular sieve.
  • a working solution of sodium aluminate with a concentration of 40 g Al 2 O 3 /L was prepared, a sodium silicate solution containing 28 wt % of SiO 2 was taken, and then diluted into a working solution of sodium silicate with a concentration of 150 g SiO 2 /L.
  • IPA/SiO 2 0.15
  • amorphous silicon-alumina precursor was added isothermal propylamine, after stirring for 1 hour at 20°C, a mixed solution containing amorphous silica-alumina precursor and template agent was obtained; after that, a mixture consisting of sodium hydroxide, silica sol and water was added to it, and the mixture was uniformly stirred to obtain silica-alumina. gel.
  • the gel obtained above was poured into a stainless steel reactor, and statically crystallized at 180° C. for 18 hours. After crystallization, after filtration and washing to neutrality, drying at 120 ° C to obtain molecular sieve product ZSM-23-2; after calcination in air at 550 ° C for 3 hours, the relative crystallinity after calcination was measured; after 600 After 2 hours of water vapor hydrothermal treatment, the hydrothermal stability was measured, and the specific properties are shown in Table 1.
  • the XRD pattern is similar to that of Fig. 1, and the scanning electron microscope image is similar to that of Fig. 2.
  • a working solution of sodium aluminate with a concentration of 50 g Al 2 O 3 /L was prepared, a sodium silicate solution containing 28 wt % of SiO 2 was taken, and then diluted into a working solution of sodium silicate with a concentration of 100 g SiO 2 /L. Take 200mL of sodium aluminate working solution and put it in the gel-forming tank, then add 60mL of sodium silicate working solution, control the reaction temperature to 30°C, and pass CO2 gas with a concentration of 50v%.
  • the gel obtained above was poured into a stainless steel reactor, and statically crystallized at 160° C. for 24 hours. After crystallization, after filtering and washing to neutrality, it was dried at 120°C to obtain the molecular sieve product ZSM-23-3; after calcination in air at 550°C for 6 hours, the relative crystallinity after calcination was measured; after 600 After 2 hours of water vapor hydrothermal treatment, the hydrothermal stability was measured, and the specific properties are shown in Table 1.
  • the XRD pattern is similar to that of Fig. 1, and the scanning electron microscope image is similar to that of Fig. 2.
  • a working solution of sodium aluminate with a concentration of 20 g Al 2 O 3 /L was prepared, and a sodium silicate solution containing 28 wt % of SiO 2 was taken, and then diluted into a working solution of sodium silicate with a concentration of 150 g SiO 2 /L. Take 300 mL of sodium aluminate working solution and put it in the gel forming tank, then add 20 mL of sodium silicate working solution, control the reaction temperature to 30 °C, and pass CO 2 gas with a concentration of 50v%.
  • amorphous silicon-alumina precursor was added iso-iso propylamine, after stirring for 1 hour at 15 °C, a mixed solution containing an amorphous silica-alumina precursor and a template agent was obtained; after that, a mixture consisting of sodium hydroxide, silica sol and water was added to it, and the mixture was uniformly stirred to obtain silica-alumina. gel.
  • the gel obtained above was poured into a stainless steel reactor, and statically crystallized at 180° C. for 24 hours. After crystallization, after filtering and washing to neutrality, drying at 120 ° C to obtain molecular sieve product ZSM-23-4; after calcining in air at 550 ° C for 4 hours, the relative crystallinity after calcination was measured; after 600 After 2 hours of water vapor hydrothermal treatment, the hydrothermal stability was measured, and the specific properties are shown in Table 1.
  • the XRD pattern is similar to that of Fig. 1, and the scanning electron microscope image is similar to that of Fig. 2.
  • a working solution of sodium aluminate with a concentration of 40 g Al 2 O 3 /L was prepared, and a sodium silicate solution containing 28 wt % of SiO 2 was taken, and then diluted into a working solution of sodium silicate with a concentration of 50 g SiO 2 /L.
  • the gel obtained above was poured into a stainless steel reactor, and statically crystallized at 180° C. for 12 hours. After crystallization, after filtration and washing to neutrality, drying at 120 °C to obtain molecular sieve product ZSM-23-5; after calcination in air at 550 °C for 3 hours, the relative crystallinity after calcination was measured; after 600 After 2 hours of water vapor hydrothermal treatment, the hydrothermal stability was measured, and the specific properties are shown in Table 1.
  • the XRD pattern is similar to that of Fig. 1, and the scanning electron microscope image is similar to that of Fig. 2.
  • a working solution of sodium aluminate with a concentration of 40 g Al 2 O 3 /L was prepared, and a sodium silicate solution containing 28 wt % of SiO 2 was taken, and then diluted into a working solution of sodium silicate with a concentration of 50 g SiO 2 /L.
  • pyrrole was added to the amorphous silicon-alumina precursor obtained above alkane, and stirred at 15°C for 1 hour to obtain a mixed solution containing amorphous silicon-alumina precursor and template agent; then, add a mixture consisting of sodium hydroxide, fumed silica, and water to it, and stir evenly to obtain Silica alumina gel.
  • the gel obtained above was poured into a stainless steel reactor, and statically crystallized at 180° C. for 12 hours. After crystallization, after filtering and washing to neutrality, it was dried at 120 °C to obtain the molecular sieve product ZSM-23-5; after calcination in air at 550 °C for 4 hours, the relative crystallinity after calcination was measured; after 600 After 2 hours of water vapor hydrothermal treatment, the hydrothermal stability was measured, and the specific properties are shown in Table 1.
  • the XRD pattern is similar to that of Fig. 1, and the scanning electron microscope image is similar to that of Fig. 2.
  • the molar ratio of Al 2 O 3 in the aluminum source: SiO 2 in the silicon source: NaOH in the alkali source: isopropylamine: H 2 O is 0.006:1:0.06:0.8:12, and the aluminum source is aluminum
  • a reaction mixture was prepared using sodium, silica sol as the silicon source, and sodium hydroxide as the alkali source.
  • the aluminum source is added to the aqueous sodium hydroxide solution, and stirred uniformly; the silicon source is added, and the mixture is uniformly stirred; and then isopropylamine is added, and the mixture is uniformly stirred to obtain a reaction mixture.
  • the resulting reaction mixture was transferred to an autoclave for hydrothermal crystallization at 170°C for 3 days.
  • reaction raw materials were added to a polytetrafluoroethylene stainless steel reaction kettle, and after dynamic crystallization at 160° C. for 10 hours, the product was suction filtered and dried to obtain the product.
  • the ratio of reaction raw materials is SiO 2 : 0.008319Al 2 O 3 : 0.27Na 2 O : 35H 2 O.
  • the product is marked as CNZSM-23-2.
  • the relative crystallinity after calcination was measured; after 2 hours of water vapor hydrothermal treatment at 600°C, the hydrothermal stability was measured. For specific properties, see Table 1.
  • a working solution of sodium aluminate with a concentration of 50 g Al 2 O 3 /L was prepared, a sodium silicate solution containing 28 wt % of SiO 2 was taken, and then diluted into a working solution of sodium silicate with a concentration of 100 g SiO 2 /L. Take 200mL of sodium aluminate working solution and put it in the gel-forming tank, then add 60mL of sodium silicate working solution, control the reaction temperature to 30°C, and pass CO2 gas with a concentration of 50v%.
  • the gel obtained above was poured into a stainless steel reactor, and statically crystallized at 160° C. for 24 hours. After the crystallization, after filtering and washing to neutrality, drying at 120 °C to obtain the original molecular sieve powder CZSM-23-3, and the relative crystallinity was measured; CZSM-23-3 was calcined in air at 550 °C for 3 hours , the relative crystallinity after calcination was measured; after 2 hours of steam hydrothermal treatment at 600 °C, the hydrothermal stability was measured, and the specific properties are shown in Table 1.
  • Solid aluminum sulfate was prepared into 60 mL of aluminum sulfate working solution (a) with a concentration of 100 g Al 2 O 3 /L.
  • the concentrated ammonia water is added with an appropriate amount of distilled water to be diluted to about 10wt% dilute ammonia water (b).
  • Take a 5-liter steel reaction tank add 0.5 liter of distilled water to the tank and heat it to 70 ° C with stirring, open the valves of the containers (a), (b) and (c) respectively, and control the flow of (a) at the same time.
  • the neutralization reaction time is 40 minutes, the flow rate of (b) is quickly adjusted to keep the pH value of the system at 7-8, and the temperature of the system is controlled at about 60°C. After the aluminum sulfate reaction was completed, the addition of (b) was stopped, and the resulting silica-alumina sol was aged at 25° C. for 40 minutes.
  • the gel obtained above was poured into a stainless steel reactor, statically crystallized at 180°C for 36 hours, then filtered and washed to neutrality, and then dried at 120°C to obtain molecular sieve CZSM-23-4, and the relative crystallinity was measured; After CZSM-23-4 was calcined in air at 550°C for 3 hours, the relative crystallinity after calcination was measured; after 600°C steam hydrothermal treatment for 2 hours, its hydrothermal stability was measured.
  • the preparation method of the embodiment of the present invention can synthesize high crystallinity, wider silicon-alumina ratio range, smaller crystal grains, more weak acid and medium-strong acid content, and has good thermal stability and hydrothermal properties.
  • Stable ZSM-23 molecular sieve is
  • Reaction raw materials decalin 90wt%, C 20 -C 30 linear alkane 10wt%.
  • reaction conditions reaction temperature 280°C; liquid space velocity 1.0h-1; hydrogen oil ratio 600; reaction hydrogen pressure 4.0MPa.
  • Comparative Example 3 Liquid yield (C 5 + ): 93%; C 20 -C 30 isomerization degree: 100%; C 20 -C 30 isomerization product yield: 42%; C 20 -C 30 isomerization The ratio of multi-branched and single-branched components in the chemical product: 0.4.
  • Example 3 Liquid yield (C 5 + ): 96%; C 20 -C 30 isomerization degree: 100%; C 20 -C 30 isomerization product yield: 58%; C 20 -C 30 isomerization The ratio of multi-branched to single-branched components in the chemical product: 2.8.

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Abstract

提供一种ZSM-23分子筛及其制备方法。ZSM-23分子筛的总酸量为0.05-0.25mmol/g，强酸含量占总酸量的5-33%，其中强酸是指在由NH 3程序升温脱附中对应脱附温度为350℃以上的酸。其制备方法包括：（1）配制含有模板剂、和无定形硅铝和/或无定形硅铝前驱物的混合溶液；（2）向步骤（1）的混合溶液中加入碱源和硅源；（3）步骤（2）中获得的物料经晶化、任选的过滤和洗涤、干燥和任选的焙烧后制得ZSM-23分子筛。该方法简单，得到的ZSM-23分子筛强酸含量低，同时具有良好的热稳定性和水热稳定性，可作为一种优异的吸附剂或催化材料。

Description

[根据细则37.2由ISA制定的发明名称]　ZSM-23分子筛及其制备方法 技术领域
本发明涉及一种ZSM-23分子筛及其制备方法和应用，具体地说，涉及一种强酸含量低的ZSM-23分子筛及其制备方法和应用。
背景技术
ZSM-23分子筛是一种高硅铝比的分子筛材料，具有MTT拓扑结构，由十元环构成其一维泪滴状孔道。凭借独特的孔道结构和可调变的酸性质，ZSM-23分子筛在分离吸附及催化领域广泛应用，发挥着不可替代的作用。尤其在石油化工产业中，其在长链烷烃及烯烃加氢裂化、烷烃及芳香烃异构等方面都有着不俗的表现，因此制备性能优良的ZSM-23分子筛具有十分重要的意义。
目前关于ZSM-23分子筛的制备方法有很多。US4076842最先公开了以吡咯烷为模板剂，合成ZSM-23分子筛的方法。之后，US4490342和US5707601相继公开了在双季铵盐(diquat-7)或小分子胺及中性胺为模板剂体系中合成ZSM-23分子筛的条件。CN101214971公开了一种纳米ZSM-23分子筛的合成方法。将铝源、硅源、氢氧化钠和异丙胺制成的反应混合物水热晶化，即可得到晶粒截面平均直径不大于100nm的ZSM-23分子筛。专利CN101613114公开了一种以ZSM-22或ZSM-23分子筛为晶种，再辅以少量乙胺、正丁胺等模板剂合成ZSM-23分子筛的方法。CN102897785则采用分步处理，先将有机模板剂或水溶液与铝源混合，在密闭反应容器中于50-190℃处理一段时间；之后向其中加入硅源、有机模板剂、水和晶种，高温水热晶化后得到HZSM-23分子筛。CN102992346中还公开了一种无模板剂合成ZSM-23分子筛的方法，将水与铝源混合后加入钠源、硅源，搅拌均匀后加入晶种水热晶化得到ZSM-23分子筛原粉。
现公开的关于ZSM-23分子筛的技术中，重点多在探寻合成新的模板剂，或对其孔道结构进行改善，或通过改进合成工艺降低生成成本。而对其酸性的调节，可采取的方法较少。文章(Journal of catalysis，1990，121，89-98)报道了以Fe原子同晶取代Al提高ZSM-23弱酸含量的方法。文章(Ind.Eng.Chem.Res.2013，52，15359-15365)采用后期加入助剂MgO调节ZSM-23酸性分布，进而调节其反应性能的方法。但这些技术对分子筛酸性的调节能力有限，制备的ZSM-23分子筛强酸含量仍然偏高，限制了ZSM-23分子筛在择形催化领域的应用。
发明内容
为了克服现有技术中的不足之处，本发明提供了一种ZSM-23分子筛及其制备方法和应用，所述ZSM-23分子筛强酸含量低，所述ZSM-23分子筛制备方法简单。
本发明涉及一种ZSM-23分子筛，所述ZSM-23分子筛的总酸量为0.05-0.25mmol/g，优选地，0.06-0.22mmol/g，更优选地，0.06-0.20mmol/g；所述ZSM-23分子筛的强酸含量占总酸量的5-33％，优选地，7-33％，更优选地，9-33％，或者进一步优选地，7-31％。进一步更优选地，10-28％；其中所述的强酸是指在由NH 3程序升温脱附(NH 3-TPD)中对应脱附温度为350℃以上的酸，其中任选地所述ZSM-23分子筛是经焙烧的或未经焙烧的。在本发明中所述ZSM-23分子筛可以是指在制备分子筛的过程中，在结晶后，经过干燥得到的产品(即，未经焙烧的)，也可以是指在制备分子筛的过程中，在结晶后，经过干燥且焙烧得到的产品(即，经焙烧的)。
上述ZSM-23分子筛中，所述ZSM-23分子筛的晶粒尺寸为100-700nm，优选晶粒尺寸为200-600nm，进一步优选晶粒尺寸为300-500nm。
上述ZSM-23分子筛中，所述ZSM-23分子筛SiO 2/Al 2O 3摩尔比为40-300，比表面积为200-400m 2/g，孔容为0.25-0.50cm 3/g；优选地，所述的ZSM-23分子筛SiO 2/Al 2O 3摩尔比为40-200或50-200，比表面积为280-370m 2/g，孔容为0.28-0.40cm 3/g。
上述ZSM-23分子筛中，所述ZSM-23分子筛相对结晶度为95-130％，经600℃水蒸汽水热处理2小时后相对结晶度为93-120％；优选相对结晶度为98-120％，经600℃水蒸汽水热处理2小时后相对结晶度为95-115％。
本发明一种ZSM-23分子筛的制备方法，所述方法包括如下内容：
(1)配制含有模板剂、和无定形硅铝和/或无定形硅铝前驱物的混合溶液；
(2)向步骤(1)的混合溶液中加入碱源、和硅源；
(3)步骤(2)中获得的物料经晶化(例如静态晶化——在没有搅拌的情况下进行晶化)、任选的过滤和洗涤、干燥、和任选的焙烧后制得ZSM-23分子筛。
上述方法步骤(1)中，所述模板剂为异丙胺、吡咯烷、N，N-二甲基甲酰胺、和二甲胺中的一种或几种。
上述方法步骤(1)中，无定形硅铝和/或无定形硅铝前驱物是基于碱性 铝源(例如，铝酸盐或偏铝酸盐，如铝酸钠、铝酸钾、偏铝酸钠、偏铝酸钾等)获得的；换言之，无定形硅铝和/或无定形硅铝前驱物不包括强酸根，如硫酸根、硝酸根等。
上述方法步骤(1)中，所述混合溶液中硅(以氧化硅计)∶铝(以氧化铝计)摩尔比为1∶(0.10-0.85)，优选为1∶(0.20-0.79)，进一步优选为1∶(0.24-0.78)；所述铝(以氧化铝计)∶模板剂的摩尔比为1∶(10-100)，优选为1∶(15-85)，进一步优选1∶(20-65)。
上述方法步骤(1)中，采用碳化法制备无定形硅铝前驱物，然后向无定形硅铝前驱物中加入模板剂得到所述的混合溶液。
本发明实施例中一种非限定性的无定形硅铝前驱物的制备过程具体如下：分别配制铝源(即碱性铝源，例如，铝酸盐如铝酸钠、铝酸钾等，优选铝酸钠)溶液和含硅化合物溶液；将铝源溶液与部分含硅化合物溶液混合，通入CO 2气体进行成胶，当通入的CO 2气体体积量占通入总体积量的50-100％时，优选为70-90％，加入所述剩余部分含硅化合物溶液，再通入剩余CO 2气体，任选经老化后制得无定形硅铝前驱物。
上述无定形硅铝前驱物制备过程中，所述剩余部分含硅化合物溶液以二氧化硅计占加入含硅化合物溶液总量以二氧化硅计的5-85wt％，优选为30-70wt％。
上述无定形硅铝前驱物制备过程中，所述成胶的反应温度为10-40℃，优选为15-35℃，控制成胶结束后的pH值为9-12。
上述无定形硅铝前驱物制备过程中，所述含硅化合物溶液为水玻璃和/或硅酸钠溶液。
上述无定形硅铝前驱物制备过程中，以Al 2O 3质量计，所述铝源溶液的浓度为15-60gAl 2O 3/L，以SiO 2质量计，所述含硅化合物溶液的浓度为40-260gSiO 2/L，所述CO 2气体的浓度为30-60v％。
上述无定形硅铝前驱物制备过程中，所述老化时间为5-60分钟，优选10-30分钟；老化温度为10-40℃，优选为15-35℃。
上述方法步骤(1)中，所述混合溶液于10-35℃搅拌0.2-1.5小时，优选10-25℃搅拌0.5-1小时。
上述方法步骤(2)中，以步骤(1)混合溶液中的铝(以氧化铝计)为基准，按SiO 2∶Al 2O 3∶R 2O(碱源，其中R为碱金属，如钠、钾)∶H 2O＝1∶(0.0025-0.025)∶(0.015-0.08)∶(30-80)、模板剂(SDA)/SiO 2＝0.10-1.8的总投料摩尔比，优选 为SiO 2/Al 2O 3为50-200，H 2O/SiO 2为30-60，R 2O/SiO 2为0.025-0.06，向步骤(1)的物料中加入碱源、补充硅源。
上述方法步骤(2)中，所述硅源为气相二氧化硅、硅溶胶和水玻璃中的一种或几种，所述碱源为氢氧化钠、氢氧化钾、和氨水中的一种或几种。
上述方法步骤(3)中，所述晶化条件为：150-200℃晶化8-72小时，优选为160-180℃晶化10-48小时；干燥温度为60-130℃，时间为2-12小时，优选为80-120℃干燥4-8小时；焙烧温度为500-600℃，时间为2-8小时，优选530-570℃焙烧3-6小时或4-6小时。
特别地，本发明公开了下述技术方案：
1.一种ZSM-23分子筛，其特征在于：所述ZSM-23分子筛的总酸量为0.05-0.25mmol/g，优选地，0.06-0.22mmol/g，更优选地，0.06-0.20mmol/g；所述ZSM-23分子筛的强酸含量占总酸量的5-33％，优选地，7-33％，更优选地，9-33％，或者进一步优选地，7-31％，进一步更优选地，10-28％；其中所述的强酸是指在由NH 3程序升温脱附(NH 3-TPD)中对应脱附温度为350℃以上的酸，其中任选地所述ZSM-23分子筛是干燥且经焙烧的样品。
2.根据前述方案中任一项所述的分子筛，其特征在于：所述ZSM-23分子筛在XRD谱图中2θ为约11.3°+/-0.3°(例如+/-0.2°或+/-0.1°)处有特征衍射峰。
3.根据前述方案中任一项所述的分子筛，其特征在于：所述ZSM-23分子筛在XRD谱图中2θ为11.2-11.5°，19.5-19.9°，20.7-21.0°，22.8-23.1°处有特征衍射峰。
4.根据前述方案中任一项所述的分子筛，其特征在于：所述ZSM-23分子筛的晶粒尺寸为100-700nm，优选晶粒尺寸为200-600nm，进一步优选晶粒尺寸为300-500nm。
5.根据前述方案中任一项所述的分子筛，其特征在于：所述ZSM-23分子筛SiO 2/Al 2O 3摩尔比为35-300，比表面积为200-400m 2/g，孔容为0.25-0.50cm 3/g；优选地，所述的ZSM-23分子筛SiO 2/Al 2O 3摩尔比为38-200，比表面积为280-370m 2/g，孔容为0.28-0.40cm 3/g。
6.根据前述方案中任一项所述的分子筛，其特征在于：所述ZSM-23分子筛焙烧后相对结晶度为95-130％，经600℃水蒸汽水热处理2小时后相对结晶度为93-120％；优选焙烧后相对结晶度为98-120％，经600℃水蒸汽水热处理2小时后相对结晶度为95-115％。
7.前述方案中任一项所述ZSM-23分子筛的制备方法，其特征在于：所述方法包括如下内容：
(1)配制含有模板剂、和无定形硅铝和/或无定形硅铝前驱物的混合溶液，优选地，无定形硅铝和/或无定形硅铝前驱物是基于碱性铝源(例如，铝酸盐或偏铝酸盐，如铝酸钠、铝酸钾、偏铝酸钠、偏铝酸钾等)获得的；
(2)向步骤(1)的混合溶液中加入碱源、和硅源；
(3)步骤(2)中获得的物料经晶化、任选的过滤和洗涤、干燥、和任选的焙烧后制得ZSM-23分子筛。
8.根据前述方案中任一项所述的方法，其特征在于：步骤(1)中，所述模板剂为异丙胺、吡咯烷、N，N-二甲基甲酰胺、和二甲胺中的一种或几种。
9.根据前述方案中任一项所述的方法，其特征在于：步骤(1)中，所述混合溶液中硅(以氧化硅计)∶铝(以氧化铝计)摩尔比为1∶(0.10-0.85)，优选为1∶(0.20-0.79)，进一步优选为1∶(0.24-0.78)；所述铝(以氧化铝计)∶模板剂的摩尔比为1∶(10-100)，优选为1∶(15-85)，进一步优选1∶(20-65)。
10.根据前述方案中任一项所述的方法，其特征在于：步骤(1)中，采用碳化法制备无定形硅铝前驱物，然后向无定形硅铝前驱物中加入模板剂得到所述的混合溶液。
11.根据前述方案中任一项所述的方法，其特征在于：步骤(1)中无定形硅铝前驱物的制备过程具体如下：分别配制铝源(例如，铝酸盐，优选铝酸钠)溶液和含硅化合物溶液；将铝源溶液与部分含硅化合物溶液混合，通入CO 2气体进行成胶，当通入的CO 2气体体积量占通入总体积量的50-100％时，优选为70-90％，加入所述剩余部分含硅化合物溶液，任选经老化后制得无定形硅铝前驱物。
12.根据前述方案中任一项所述的方法，其特征在于：所述剩余部分含硅化合物溶液以二氧化硅计占加入含硅化合物溶液总量以二氧化硅计的5-85wt％，优选为30-70wt％。
13.根据前述方案中任一项所述的方法，其特征在于：所述成胶的反应温度为10-40℃，优选为15-35℃，控制成胶结束后的pH值为9-12。
14.根据前述方案中任一项所述的方法，其特征在于：所述含硅化合物溶液为水玻璃和/或硅酸钠溶液。
15.根据前述方案中任一项所述的方法，其特征在于：以Al 2O 3质量 计，所述铝源溶液的浓度为15-60gAl 2O 3/L，以SiO 2质量计，所述含硅化合物溶液的浓度为40-260gSiO 2/L，所述CO 2气体的浓度为30-60v％。
16.根据前述方案中任一项所述的方法，其特征在于：所述老化时间为5-60分钟，优选10-30分钟；老化温度为10-40℃，优选为15-35℃。
17.根据前述方案中任一项所述的方法，其特征在于：步骤(1)中，所述混合溶液于10-35℃搅拌0.2-1.5小时，优选10-25℃搅拌0.5-1小时。
18.根据前述方案中任一项所述的方法，其特征在于：步骤(2)中，以步骤(1)混合溶液中的铝(以氧化铝计)为基准，按SiO 2∶Al 2O 3∶R 2O(碱源，其中R为碱金属，如钠、钾)∶H 2O＝1∶(0.0025-0.025)∶(0.015-0.08)∶(30-80)、模板剂(SDA)/SiO 2＝0.10-1.8的总投料摩尔比，优选为SiO 2/Al 2O 3为50-200，H 2O/SiO 2为30-60，R 2O/SiO 2为0.025-0.06，向步骤(1)的物料中加入碱源、补充硅源。
19.根据前述方案中任一项所述的方法，其特征在于：步骤(2)中，所述硅源为气相二氧化硅、硅溶胶和水玻璃中的一种或几种，所述碱源为氢氧化钠、氢氧化钾、和氨水中的一种或几种。
20.根据前述方案中任一项所述的方法，其特征在于：步骤(3)中，所述晶化条件为：150-200℃晶化8-72小时，优选为160-180℃晶化10-48小时；干燥温度为60-130℃，时间为2-12小时，优选为80-120℃干燥4-8小时；焙烧温度为500-600℃，时间为2-8小时，优选530-570℃焙烧3-6小时或4-6小时。
与现有技术相比，本发明具有以下优点：
本发明提供的ZSM-23分子筛的制备方法，无定形硅铝前驱物的制备过程中，加入了合成所需全部铝源，促进了分子筛初级结构单元的生成；且当向无定形硅铝前驱物中加入模板剂时，模板剂会优先与Al物种鳌合，之后吸附在形成的初级结构单元表面，实现分子筛结构的预组装，生成大量晶核；同时能更好地控制Al原子的结合位点，有助于后期晶化制得具有更多弱酸及中强酸位的ZSM-23。当补充硅源加入形成最终凝胶后，经静态晶化，大量晶核可快速生长成高结晶度、晶粒尺寸小的ZSM-23分子筛。此外，本发明方法扩展了ZSM-23的合成硅铝比区间，缩短了分子筛的晶化时间，降低了ZSM-23分子筛合成过程中模板剂用量，得到的分子筛产品性能优良，是一种绿色可行的工业生产路线。
本发明方法合成的ZSM-23分子筛样品结晶度高、晶粒尺寸较小，具 有更多的弱酸及中强酸，强酸含量低，同时具有良好的热稳定性和水热稳定性，可作为一种优异的吸附剂或催化材料。
附图说明
图1为本发明合成产品的XRD谱图。
图2为本发明合成产品的扫描电镜图片。
具体实施方式
本发明分析方法：
比表面积和孔容由美国Micromeritics公司ASAP 2405型物理吸附仪采用低温液氮物理吸附法测定。
硅铝摩尔比采用化学分析法测定。
采用日本理学公司生产的Dmax2500型X射线衍射仪采集样品的XRD谱图。分子筛的相对结晶度由X射线粉末衍射法(XRD)测定，具体以常规ZSM-23分子筛XRD谱图中2θ为约11.3、19.5-23°处衍射峰的高度之和作为结晶度100％，其它样品与之对比得到相对结晶度。
根据本发明，ZSM-23分子筛在XRD谱图中2θ为约11.3°+/-0.3°(例如+/-0.2°或+/-0.1°)处有特征衍射峰。
根据本发明，ZSM-23分子筛在XRD谱图中2θ为11.2-11.5°，19.5-19.9°，20.7-21.0°，22.8-23.1°处有特征衍射峰。
晶粒尺寸由日本JEOL公司的JSM-7500F场发射扫描电镜获得。
酸分布(包括总酸量和强酸含量)由NH 3程序升温脱附(NH 3-TPD)测得，其中脱附温度为350℃以上对应的酸量作为强酸量。
本发明中，酸量以H +计。
本发明中，wt％为质量分数，v％为体积分数。
为了更好地说明本发明，下面结合实施例和对比例来进一步说明本发明。但本发明的范围不只限于这些实施例的范围。
实施例1
配制浓度为40gAl 2O 3/L铝酸钠工作溶液，取含SiO 228wt％的硅酸钠溶液，再稀释成浓度为100gSiO 2/L硅酸钠工作溶液。取150mL铝酸钠工作溶液置于成胶罐中，然后加入50mL硅酸钠工作溶液，控制反应温度20℃，通入浓度为50v％的CO 2气体，当pH值达到10.0时停止通CO 2，再加入90mL硅酸钠工作溶液，然后通入剩余CO 2气体稳定，在25℃下老化30分钟后，得到无定形硅铝前驱物。按 SiO 2∶Al 2O 3∶Na 2O∶H 2O＝1∶0.02∶0.04∶45、IPA/SiO 2＝0.7的总投料摩尔比(IPA为模板剂异丙胺)，向上述所得的无定形硅铝前驱物中加入异丙胺，于15℃搅拌0.8小时后，得到含有无定形硅铝前驱物与模板剂的混合溶液；之后，再向其中加入由氢氧化钠、硅溶胶、水组成的混合物，搅拌均匀，得到硅铝凝胶。
将上述所得凝胶倒入不锈钢反应釜中，于160℃静态晶化20小时。晶化结束后，经过滤、洗涤至中性后，在120℃下干燥，得分子筛产品ZSM-23-1；经550℃空气中焙烧3小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。图1为分子筛的XRD谱图，图2为分子筛的扫描电镜图片，证实所获得的分子筛为ZSM-23分子筛。
实施例2
配制浓度为40gAl 2O 3/L铝酸钠工作溶液，取含SiO 228wt％的硅酸钠溶液，再稀释成浓度为150 gSiO 2/L硅酸钠工作溶液。取200mL铝酸钠工作溶液置于成胶罐中，然后加入40mL硅酸钠工作溶液，控制反应温度25℃，通入浓度为50v％的CO 2气体，当pH值达到10.5时停止通CO 2，再加入40mL硅酸钠工作溶液，然后通入剩余CO 2气体稳定，在20℃下老化20分钟后，得到无定形硅铝前驱物。按SiO 2∶Al 2O 3∶Na 2O∶H 2O＝1∶0.005∶0.04∶60、IPA/SiO 2＝0.15的总投料摩尔比，向上述所得的无定形硅铝前驱物中加入异丙胺，于20℃搅拌1小时后，得到含有无定形硅铝前驱物与模板剂的混合溶液；之后，再向其中加入由氢氧化钠、硅溶胶、水组成的混合物，搅拌均匀，得到硅铝凝胶。
将上述所得凝胶倒入不锈钢反应釜中，于180℃静态晶化18小时。晶化结束后，经过滤、洗涤至中性后，在120℃下干燥，得分子筛产品ZSM-23-2；经550℃空气中焙烧3小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。其XRD谱图与图1类似，扫描电镜图片与图2类似。
实施例3
配制浓度为50gAl 2O 3/L铝酸钠工作溶液，取含SiO 228wt％的硅酸钠溶液，再稀释成浓度为100 gSiO 2/L硅酸钠工作溶液。取200mL铝酸钠工作溶液置于成胶罐中，然后加入60mL硅酸钠工作溶液，控制反应温度30℃，通入浓度为50v％的CO 2气体，当pH值达到10.0时停止通CO 2， 再加入40mL硅酸钠工作溶液，然后通入剩余CO 2气体稳定，在35℃下老化15分钟后，得到无定形硅铝前驱物。按SiO 2∶Al 2O 3∶Na 2O∶H 2O＝1∶0.01∶0.04∶30、IPA/SiO 2＝0.4的总投料摩尔比，向上述所得的无定形硅铝前驱物中加入异丙胺，于25℃搅拌0.5小时后，得到含有无定形硅铝前驱物与模板剂的混合溶液；之后，再向其中加入由氢氧化钠、硅溶胶、水组成的混合物，搅拌均匀，得到硅铝凝胶。
将上述所得凝胶倒入不锈钢反应釜中，于160℃静态晶化24小时。晶化结束后，经过滤、洗涤至中性后，在120℃下干燥，得分子筛产品ZSM-23-3；经550℃空气中焙烧6小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。其XRD谱图与图1类似，扫描电镜图片与图2类似。
实施例4
配制浓度为20gAl 2O 3/L铝酸钠工作溶液，取含SiO 228wt％的硅酸钠溶液，再稀释成浓度为150 gSiO 2/L硅酸钠工作溶液。取300mL铝酸钠工作溶液置于成胶罐中，然后加入20mL硅酸钠工作溶液，控制反应温度30℃，通入浓度为50v％的CO 2气体，当pH值达到11.0时停止通CO 2，再加入20mL硅酸钠工作溶液，然后通入剩余CO 2气体稳定，在20℃下老化30分钟后，得到无定形硅铝前驱物。按SiO 2∶Al 2O 3∶Na 2O∶H 2O＝1∶0.01∶0.04∶45、IPA/SiO 2＝0.3的总投料摩尔比，向上述所得的无定形硅铝前驱物中加入异丙胺，于15℃搅拌1小时后，得到含有无定形硅铝前驱物与模板剂的混合溶液；之后，再向其中加入由氢氧化钠、硅溶胶、水组成的混合物，搅拌均匀，得到硅铝凝胶。
将上述所得凝胶倒入不锈钢反应釜中，于180℃静态晶化24小时。晶化结束后，经过滤、洗涤至中性后，在120℃下干燥，得分子筛产品ZSM-23-4；经550℃空气中焙烧4小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。其XRD谱图与图1类似，扫描电镜图片与图2类似。
实施例5
配制浓度为40gAl 2O 3/L铝酸钠工作溶液，取含SiO 228wt％的硅酸钠溶液，再稀释成浓度为50gSiO 2/L硅酸钠工作溶液。取150mL铝酸钠工作溶液置于成胶罐中，然后加入140mL硅酸钠工作溶液，控制反应温度25℃，通入浓度为50v％的CO 2气体，当pH值达到10.0时停止通CO 2，再加入 140mL硅酸钠工作溶液，然后通入剩余CO 2气体稳定，在25℃下老化20分钟后，得到无定形硅铝前驱物。按SiO 2∶Al 2O 3∶Na 2O∶H 2O＝1∶0.01∶0.04∶45、IPA/SiO 2＝0.4的总投料摩尔比，向上述所得的无定形硅铝前驱物中加入异丙胺，于15℃搅拌1小时后，得到含有无定形硅铝前驱物与模板剂的混合溶液；之后，再向其中加入由氢氧化钠、气相二氧化硅、水组成的混合物，搅拌均匀，得到硅铝凝胶。
将上述所得凝胶倒入不锈钢反应釜中，于180℃静态晶化12小时。晶化结束后，经过滤、洗涤至中性后，在120℃下干燥，得分子筛产品ZSM-23-5；经550℃空气中焙烧3小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。其XRD谱图与图1类似，扫描电镜图片与图2类似。
实施例6
配制浓度为40gAl 2O 3/L铝酸钠工作溶液，取含SiO 228wt％的硅酸钠溶液，再稀释成浓度为50 gSiO 2/L硅酸钠工作溶液。取150mL铝酸钠工作溶液置于成胶罐中，然后加入140mL硅酸钠工作溶液，控制反应温度25℃，通入浓度为50v％的CO 2气体，当pH值达到10.0时停止通CO 2，再加入140mL硅酸钠工作溶液，然后通入剩余CO 2气体稳定，在25℃下老化20分钟后，得到无定形硅铝前驱物。按SiO 2∶Al 2O 3∶Na 2O∶H 2O＝1∶0.01∶0.04∶45、SDA/SiO 2＝0.1的总投料摩尔比，向上述所得的无定形硅铝前驱物中加入吡咯烷，于15℃搅拌1小时后，得到含有无定形硅铝前驱物与模板剂的混合溶液；之后，再向其中加入由氢氧化钠、气相二氧化硅、水组成的混合物，搅拌均匀，得到硅铝凝胶。
将上述所得凝胶倒入不锈钢反应釜中，于180℃静态晶化12小时。晶化结束后，经过滤、洗涤至中性后，在120℃下干燥，得分子筛产品ZSM-23-5；经550℃空气中焙烧4小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。其XRD谱图与图1类似，扫描电镜图片与图2类似。
比较例1(参照CN101214971A)
按摩尔比铝源中的Al 2O 3∶硅源中的SiO 2∶碱源中的NaOH∶异丙胺∶H 2O为0.006∶1∶0.06∶0.8∶12备料，所述的铝源是铝酸钠，硅源是硅溶胶，碱源为氢氧化钠，制备反应混合物。先将铝源加入到氢氧化钠水溶液中，搅拌均匀；加入硅源，搅拌均匀；再加入异丙胺，搅拌均匀，得到反应混合物。 将制得的反应混合物转移至高压反应釜中于170℃水热晶化3天。然后过滤、洗涤至中性后，在120℃下干燥，得分子筛产品CNZSM-23-1；CNZSM-23-1经550℃空气中焙烧3小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。
比较例2(参照CN102992346A)
将8.12gH 2O与0.092g硫酸铝混合均匀，再向其中加入0.38gNaOH，之后再搅拌下加入3.32g二氧化硅含量为30.5％的硅溶胶，继续搅拌直到溶液变均匀后，加入10％ZSM-23分子筛做晶种(晶种量以占投入SiO 2的质量百分比计算)。将反应原料加入聚四氟乙烯不锈钢反应釜中，160℃动态晶化10小时后，将产物抽滤，烘干后得到产品。反应原料配比为SiO 2∶0.008319Al 2O 3∶0.27Na 2O∶35H 2O。产品标记为CNZSM-23-2，经550℃空气中焙烧3小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。
比较例3
配制浓度为50gAl 2O 3/L铝酸钠工作溶液，取含SiO 228wt％的硅酸钠溶液，再稀释成浓度为100 gSiO 2/L硅酸钠工作溶液。取200mL铝酸钠工作溶液置于成胶罐中，然后加入60mL硅酸钠工作溶液，控制反应温度30℃，通入浓度为50v％的CO 2气体，当pH值达到10.0时停止通CO 2，再加入40mL硅酸钠工作溶液，然后通入剩余CO 2气体稳定，在25℃下老化30分钟后，得到无定形硅铝前驱物。按SiO 2∶Al 2O 3∶Na 2O∶H 2O＝1∶0.01∶0.04∶30、IPA/SiO 2＝0.4的总投料摩尔比，向上述所得的无定形硅铝前驱物中加入由氢氧化钠、硅溶胶、异丙胺、水组成的混合物，搅拌均匀，得到硅铝凝胶。
将上述所得凝胶倒入不锈钢反应釜中，于160℃静态晶化24小时。晶化结束后，经过滤、洗涤至中性后，在120℃下干燥，得分子筛原粉CZSM-23-3，测得相对结晶度；CZSM-23-3经550℃空气中焙烧3小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。
比较例4
将固体硫酸铝配制成60mL浓度为100gAl 2O 3/L的硫酸铝工作溶液(a)。将浓氨水加入适量蒸馏水稀释成约10wt％稀氨水(b)。取含SiO 228wt％的硅酸钠溶液，再稀释成140mL浓度为100gSiO 2/L硅酸钠工作溶液(c)。取 一5升的钢制反应罐，罐中加入0.5升蒸馏水并搅拌加热至70℃后，同时打开分别存有(a)、(b)和(c)容器的阀门，控制(a)的流量以使中和反应时间在40分钟，并迅速调整(b)的流量使体系的pH值保持在7-8，并控制体系的温度在60℃左右。硫酸铝反应完成后，停止加入(b)，生成的硅铝溶胶于25℃老化40分钟。按SiO 2∶Al 2O 3∶Na 2O∶H 2O＝1∶0.02∶0.04∶45、IPA/SiO 2＝0.7的总投料摩尔比，向上述所得的无定形硅铝前驱物中加入异丙胺，于15℃搅拌0.8小时后，得到含有无定形硅铝前驱物与模板剂的混合溶液；之后，再向其中加入由氢氧化钠、硅溶胶、水组成的混合物，搅拌均匀，得到硅铝凝胶。
将上述所得凝胶倒入不锈钢反应釜中，在180℃静态晶化36小时，然后过滤、洗涤至中性后，在120℃下干燥，得分子筛CZSM-23-4，测得相对结晶度；CZSM-23-4经550℃空气中焙烧3小时后，测得焙烧后的相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。
对比例5(常规ZSM-23分子筛的制备)
将水玻璃、硫酸铝、异丙胺(IPA)、氢氧化钠与水混合制得总摩尔配比为硅源中SiO 2∶铝源中Al 2O 3∶NaOH∶IPA∶H 2O＝1∶0.01∶0.08∶1.0∶50的凝胶，于180℃加热72h后，经过滤、洗涤、干燥、焙烧后，测得其相对结晶度；经600℃水蒸汽水热处理2小时后，测得其水热稳定性，具体性质见表1。
Figure PCTCN2022070636-appb-000001
由表1的数据可知：本发明实施例的制备方法，可以合成出高结晶度、硅铝比区间更广、晶粒更小、弱酸及中强酸含量更多且具有良好热稳定性和水热稳定性的ZSM-23分子筛。
在固定床微型反应器上对ZSM-23分子筛样品性能进行评价。对比例3与实施例3在直链C 20-C 30加氢异构反应中的反应条件及催化结果如下：
反应原料：十氢萘90wt％，C 20-C 30直链烷烃10wt％。
反应条件：反应温度280℃；液体空速1.0h-1；氢油比600；反应氢压4.0MPa。
对比例3：液收(C 5 +)：93％；C 20-C 30异构化程度：100％；C 20-C 30异构化产品收率：42％；C 20-C 30异构化产品中多支链与单支链组分的比例：0.4。
实施例3：液收(C 5 +)：96％；C 20-C 30异构化程度：100％；C 20-C 30异构化产品收率：58％；C 20-C 30异构化产品中多支链与单支链组分的比例：2.8。

Claims (18)

  1. 一种ZSM-23分子筛，其特征在于：所述ZSM-23分子筛的总酸量为0.05-0.25mmol/g，优选地，0.06-0.22mmol/g，更优选地，0.06-0.20mmol/g；所述ZSM-23分子筛的强酸含量占总酸量的5-33％，优选地，7-33％，更优选地，9-33％，或者进一步优选地，7-31％，进一步更优选地，10-28％；其中所述的强酸是指在由NH 3程序升温脱附(NH 3-TPD)中对应脱附温度为350℃以上的酸，其中任选地所述ZSM-23分子筛是干燥且经焙烧的样品。
  2. 根据前述权利要求中任一项所述的分子筛，其特征在于：所述ZSM-23分子筛的晶粒尺寸为100-700nm，优选晶粒尺寸为200-600nm，进一步优选晶粒尺寸为300-500nm。
  3. 根据前述权利要求中任一项所述的分子筛，其特征在于：所述ZSM-23分子筛SiO 2/Al 2O 3摩尔比为35-300，比表面积为200-400m 2/g，孔容为0.25-0.50cm 3/g；优选地，所述的ZSM-23分子筛SiO 2/Al 2O 3摩尔比为38-200，比表面积为280-370m 2/g，孔容为0.28-0.40cm 3/g。
  4. 根据前述权利要求中任一项所述的分子筛，其特征在于：所述ZSM-23分子筛焙烧后相对结晶度为95-130％，经600℃水蒸汽水热处理2小时后相对结晶度为93-120％；优选焙烧后相对结晶度为98-120％，经600℃水蒸汽水热处理2小时后相对结晶度为95-115％。
  5. 前述权利要求中任一项所述ZSM-23分子筛的制备方法，其特征在于：所述方法包括如下内容：
    (1)配制含有模板剂、和无定形硅铝和/或无定形硅铝前驱物的混合溶液，优选地，无定形硅铝和/或无定形硅铝前驱物是基于碱性铝源(例如，铝酸盐或偏铝酸盐，如铝酸钠、铝酸钾、偏铝酸钠、偏铝酸钾等)获得的；
    (2)向步骤(1)的混合溶液中加入碱源、和硅源；
    (3)步骤(2)中获得的物料经晶化、任选的过滤和洗涤、干燥、和任选的焙烧后制得ZSM-23分子筛。
  6. 根据权利要求5所述的方法，其特征在于：步骤(1)中，所述模板剂为异丙胺、吡咯烷、N，N-二甲基甲酰胺、和二甲胺中的一种或几种。
  7. 根据前述权利要求5-6中任一项所述的方法，其特征在于：步骤(1)中，所述混合溶液中硅(以氧化硅计)∶铝(以氧化铝计)摩尔比为1∶(0.10-0.85)，优选为1∶(0.20-0.79)，进一步优选为1∶(0.24-0.78)；所述铝(以氧化铝计)∶模板剂的摩尔比为1∶(10-100)，优选为1∶(15-85)，进一步优选 1∶(20-65)。
  8. 根据前述权利要求5-7中任一项所述的方法，其特征在于：步骤(1)中，采用碳化法制备无定形硅铝前驱物，然后向无定形硅铝前驱物中加入模板剂得到所述的混合溶液。
  9. 根据前述权利要求5-8中任一项所述的方法，其特征在于：步骤(1)中无定形硅铝前驱物的制备过程具体如下：分别配制铝源(例如，铝酸盐，优选铝酸钠)溶液和含硅化合物溶液；将铝源溶液与部分含硅化合物溶液混合，通入CO 2气体进行成胶，当通入的CO 2气体体积量占通入总体积量的50-100％时，优选为70-90％，加入所述剩余部分含硅化合物溶液，任选经老化后制得无定形硅铝前驱物。
  10. 根据权利要求9所述的方法，其特征在于：所述剩余部分含硅化合物溶液以二氧化硅计占加入含硅化合物溶液总量以二氧化硅计的5-85wt％，优选为30-70wt％。
  11. 根据前述权利要求9-10中任一项所述的方法，其特征在于：所述成胶的反应温度为10-40℃，优选为15-35℃，控制成胶结束后的pH值为9-12。
  12. 根据前述权利要求9-11中任一项所述的方法，其特征在于：所述含硅化合物溶液为水玻璃和/或硅酸钠溶液。
  13. 根据前述权利要求9-12中任一项所述的方法，其特征在于：以Al 2O 3质量计，所述铝源溶液的浓度为15-60gAl 2O 3/L，以SiO 2质量计，所述含硅化合物溶液的浓度为40-260gSiO 2/L，所述CO 2气体的浓度为30-60v％。
  14. 根据前述权利要求9-13中任一项所述的方法，其特征在于：所述老化时间为5-60分钟，优选10-30分钟；老化温度为10-40℃，优选为15-35℃。
  15. 根据前述权利要求5-14中任一项所述的方法，其特征在于：步骤(1)中，所述混合溶液于10-35℃搅拌0.2-1.5小时，优选10-25℃搅拌0.5-1小时。
  16. 根据前述权利要求5-15中任一项所述的方法，其特征在于：步骤(2)中，以步骤(1)混合溶液中的铝(以氧化铝计)为基准，按SiO 2∶Al 2O 3∶R 2O(碱源，其中R为碱金属，如钠、钾)∶H 2O＝1∶(0.0025-0.025)∶(0.015-0.08)∶(30-80)、模板剂(SDA)/SiO 2＝0.10-1.8的总投料摩尔比，优选 为SiO 2/Al 2O 3为50-200，H 2O/SiO 2为30-60，R 2O/SiO 2为0.025-0.06，向步骤(1)的物料中加入碱源、补充硅源。
  17. 根据前述权利要求5-16中任一项所述的方法，其特征在于：步骤(2)中，所述硅源为气相二氧化硅、硅溶胶和水玻璃中的一种或几种，所述碱源为氢氧化钠、氢氧化钾、和氨水中的一种或几种。
  18. 根据前述权利要求5-17中任一项所述的方法，其特征在于：步骤(3)中，所述晶化条件为：150-200℃晶化8-72小时，优选为160-180℃晶化10-48小时；干燥温度为60-130℃，时间为2-12小时，优选为80-120℃干燥4-8小时；焙烧温度为500-600℃，时间为2-8小时，优选530-570℃焙烧3-6小时或4-6小时。
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