CN112675905A - Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application - Google Patents

Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application Download PDF

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CN112675905A
CN112675905A CN201910992833.3A CN201910992833A CN112675905A CN 112675905 A CN112675905 A CN 112675905A CN 201910992833 A CN201910992833 A CN 201910992833A CN 112675905 A CN112675905 A CN 112675905A
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molecular sieve
catalyst
oxide
mixed oxide
sapo
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焦文千
王仰东
刘苏
周海波
苏俊杰
刘畅
张琳
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention discloses a catalyst for preparing low-carbon olefin from synthesis gas. The catalyst comprises metal oxide and SAPO molecular sieve, wherein the SAPO molecular sieve is in a sheet shape, and the thickness of the SAPO molecular sieve is less than 100 nm. The invention also discloses application of the catalyst in preparation of low-carbon olefin from synthesis gas. When the catalyst is used for preparing low-carbon olefin from synthesis gas, the conversion activity and the olefin selectivity can be obviously improved.

Description

Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a catalyst for preparing low-carbon olefin from synthesis gas, a preparation method and application.
Background
The synthesis gas is a mixed gas of carbon monoxide and hydrogen, and is an important platform compound for converting and utilizing coal, natural gas and organic solid wastes. Starting from the synthesis gas, various chemical products can be prepared, including oil products, wax, olefin, aromatic hydrocarbon and the like. Among them, low-carbon olefins (ethylene, propylene) are basic raw materials of many chemical products, and the production level and yield thereof mark the economic development level of a country. Therefore, research on the production of light olefins by conversion of syngas is particularly concerned by scientists.
The synthesis gas can be efficiently converted to prepare the low-carbon olefin through the conventional Fischer-Tropsch synthesis process. The Fischer-Tropsch process mostly adopts supported iron or cobalt as a catalyst, and the carbon monoxide conversion capability is strong. CN103157489A discloses a catalyst for directly preparing low-carbon olefin from synthesis gas, and a preparation method and application thereof. The catalyst adopts a coprecipitation method to highly disperse Fe and an auxiliary agent on the surface of an alkaline carrier, and in the direct conversion process of synthesis gas, the single-pass conversion rate of CO can reach 75-85%, and the weight of olefin in an organic product can reach 50-60%. Literature [ science.2012,335,835]Reports a catalyst for efficiently preparing low-carbon olefinThe catalyst, by highly dispersing the nano-iron particles on inert alpha-alumina or carbon fibers, finally achieves an olefin selectivity of over 60%. CN1083415A discloses a catalyst for preparing low-carbon olefins such as ethylene and propylene with high selectivity from synthesis gas, which mainly uses alkaline earth metal oxide or high-silicon zeolite molecular sieve (or phosphorus-aluminum zeolite) as a carrier, supported iron-manganese as a catalyst active center, and alkali metal K or Cs ions as an auxiliary agent, so that the conversion of the CO raw material can be realized by more than 90%, and the olefin selectivity can reach more than 66%. However, because of the limitation of the reaction characteristics of the Fischer-Tropsch synthesis process, the low-carbon olefin prepared by the process is often wide in product distribution (ASF) and low in single selectivity of the olefin. Then, scientists couple the methanol synthesis catalyst (oxide) with the methanol conversion olefin catalyst (SAPO molecular sieve) to achieve the purpose of direct and efficient conversion of the synthesis gas. Literature [ science.2016,351,1065]An OX-ZEO process is reported, which can obviously improve the selectivity of low-carbon olefin. The process core lies in a dual-functional composite catalyst ZnCrOx/SAPO. In one aspect, partially oxidized ZnCrOx (zinc chromium oxide) activates CO and H2(ii) a In another aspect, the C-C coupling is carried out within the acid-restricted channels of the zeolite. The catalyst has an ultra-high selectivity (80% olefins, 14% alkanes) up to 94% for the direct conversion of syngas to (C2-C4), with only 2% methane, with a CO conversion of 17%. Literature [ Angew. chem. int. Ed.2016,55,1]A dual-function catalyst is reported, methanol synthesis reaction is coupled with C-C coupling (methanol to olefin) reaction, the Zr-Zn/SAPO-34 dual-function catalyst is successfully designed, and breakthrough is made in the aspect of low-carbon olefin selectivity. Under the milder condition (1MPa/400 ℃/H)2: CO is 2: 1) the selectivity of the low-carbon olefin reaches 74 percent, and the conversion rate of CO is 11 percent. Literature [ chem.cat.chem 2018,10,1536]Reports a Zr-In2O3SAPO-34 coupling system at 2MPa/400 ℃/H2: 1-CO: 1, the CO conversion rate is 27.7 percent, and the olefin selectivity is 73.6 percent.
In summary, the modified fischer-tropsch catalysts of the prior art have higher CO conversion efficiency, but the product selectivity is limited by the ASF distribution (58%), and the olefin selectivity cannot be further improved, which seriously hinders further application of the process. The novel coupling catalyst system can realize the high-selectivity preparation of low-carbon olefin from synthesis gas, but the CO conversion rate is not high, and the design and preparation of the coupling catalyst system with high CO conversion rate and high olefin selectivity have very wide industrial application value.
Disclosure of Invention
The invention aims to solve the problems of low reaction activity, low CO conversion rate, low selectivity of low-carbon olefin and low alkene ratio in a product in the prior art, and provides a catalyst for preparing low-carbon olefin from synthesis gas, a preparation method and application. When the catalyst is used for preparing low-carbon olefin from synthesis gas, the conversion activity and the olefin selectivity can be obviously improved.
The invention provides a catalyst for preparing low-carbon olefin from synthesis gas, which comprises a metal oxide and an SAPO molecular sieve, wherein the SAPO molecular sieve is in a sheet shape, and the thickness of the SAPO molecular sieve is less than 100nm, preferably 5-100 nm.
In the above technical solution, the particle size of the SAPO molecular sieve is below 2000nm, preferably 100-1000nm, and more preferably 200-800 nm.
In the above technical scheme, the Si/Al molar ratio of the SAPO molecular sieve is 0.001-0.20, preferably 0.001-0.15, and more preferably 0.01-0.10.
In the above technical scheme, the SAPO molecular sieve is preferably an SAPO-34 molecular sieve.
In the above technical solution, the metal oxide is selected from one or more of zinc oxide, zinc-chromium mixed oxide, zinc-zirconium mixed oxide, indium oxide, zirconium oxide, indium-zirconium mixed oxide, manganese-chromium mixed oxide, manganese-aluminum mixed oxide, manganese-zirconium mixed oxide, cobalt-aluminum mixed oxide, iron-aluminum mixed oxide, and cerium oxide.
In the above-described embodiment, the metal oxide is preferably an oxide such as a zinc-chromium mixed oxide, a zinc-aluminum mixed oxide, an indium-zirconium mixed oxide, a manganese-chromium mixed oxide, a manganese-aluminum mixed oxide, a manganese-zirconium mixed oxide, a cobalt-aluminum mixed oxide, or an iron-aluminum mixed oxide, and more preferably one or more of a zinc-chromium mixed oxide, a zinc-zirconium mixed oxide, a zinc-aluminum mixed oxide, and an indium-zirconium mixed oxide.
In the technical scheme, the mass ratio of the metal oxide to the SAPO molecular sieve is 1: 8-8: 1, preferably 1: 2-2: 1.
in the above technical solutions, the metal oxide and the SAPO molecular sieve are present in a form independent of each other, such as independent packages or mechanical mixtures with each other.
The second aspect of the present invention provides a method for preparing a catalyst for preparing low carbon olefins from synthesis gas, comprising: respectively preparing metal oxide and SAPO molecular sieve, and mixing the metal oxide and the SAPO molecular sieve to obtain the catalyst.
In the above technical scheme, the metal oxide can be prepared by a conventional method, such as a precipitation method.
In the above technical scheme, the preparation method of the SAPO molecular sieve comprises:
uniformly mixing a phosphorus source, an aluminum source, a silicon source, a template agent and water according to a proportion to obtain mixed gel; and putting the mixed gel into a reaction kettle for hydrothermal crystallization to obtain the SAPO molecular sieve.
In the technical scheme, in the preparation method of the SAPO molecular sieve, the phosphorus source is P2O5The aluminum source is calculated as Al2O3The silicon source is calculated by SiO2The template agent and the water meet the following molar ratio: p2O5：Al2O3：SiO2: template agent: h2O＝(0.85-3.0)：1：(0.0001-0.4)：(1.5-3.0)：(20-100)。
In the technical scheme, the phosphorus source is one or a mixture of several of phosphoric acid, phosphorous acid, phosphate and phosphorus oxide; the aluminum source is one or a mixture of more of pseudo-boehmite, aluminum sol, aluminum isopropoxide, aluminum tert-butoxide and aluminate; the template agent is one or a mixture of more of tetraethyl ammonium hydroxide, triethylamine, diethylamine, N-diisopropylethylamine, morpholine, cyclohexylamine, N-propylamine, isopropylamine, di-N-propylamine, diisopropylamine, tripropylamine, N-butylamine or isobutylamine.
In a third aspect of the present invention, a method for preparing low carbon olefins from synthesis gas is provided, wherein synthesis gas contacts with the above catalyst to react, so as to obtain a product containing low carbon olefins.
In the above technical scheme, the reaction conditions are as follows: the reaction temperature is 320-500 ℃, the reaction pressure is 0.5-8MPa, and the volume space velocity is 1000-9600h-1In syngas, CO and H2The volume ratio of (A) to (B) is 0.3 to 3.5.
Compared with the existing catalyst, the inventor unexpectedly finds that when the nano flaky SAPO molecular sieve is coupled with the metal oxide, the CO conversion rate and the olefin selectivity can be remarkably improved when the nano flaky SAPO molecular sieve is used for preparing low-carbon olefins from synthesis gas, the low-carbon alkane selectivity is inhibited, and the catalyst has a higher alkene-alkane ratio. The catalyst of the invention has simple preparation method, cheap and easily obtained raw materials and low preparation cost.
Drawings
FIG. 1 is an XRD pattern of the molecular sieve obtained by the method of example 4;
FIG. 2 is a scanning electron micrograph of a molecular sieve obtained by the method of example 4;
FIG. 3 is a scanning electron micrograph of the molecular sieve obtained by the method of comparative example 4.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, but the scope of the present invention is not limited by the examples. In the present invention, wt% is a mass fraction.
The test conditions of XRD and scanning electron microscope in the invention are as follows:
test conditions of XRD: the crystal phase analysis of the molecular sieve was carried out by using an X-ray diffractometer of Rigaku-Ultima type in Japan. CuK α radiation, wavelength λ 0.15432 nm. The scanning range of the X-ray diffraction pattern is 2 theta 5-50 degrees, and the scanning speed is 10 DEG/min.
The test conditions of the scanning electron microscope are as follows: and analyzing the size and the shape of the sample by adopting a Hitachi S-4800 cold field emission high-resolution scanning electron microscope of Hitachi, Japan.
[ example 1 ]
ZnCrOxThe mixed oxide is prepared by the following steps:
weighing equal amount of Cr (NO)3)3·9H2O and Zn (NO)3)2·6H2Dispersing the solid O in water, and stirring until the solid O is completely dissolved; weighing a certain amount of (NH)4)2CO3The solid was dissolved in water to prepare a 0.1M solution. Dropping the two aqueous solutions into a beaker at the same time for coprecipitation, filtering and washing the precipitate, drying the precipitate at 100 ℃ overnight, and roasting the precipitate at 500 ℃ for 4 h.
The sheet SAPO molecular sieve is prepared by the following steps:
10.2 g of aluminum isopropoxide powder was dispersed in 59.9 g of tetraethylammonium hydroxide (TEAOH, 25 wt% strength) solution and stirred until completely dissolved; 11.6 g of phosphoric acid (85 wt% in concentration) was added to the above solution, and stirring was continued at room temperature; 0.15 g of silica Sol (SiO)240 wt%) was added to the above solution, stirred at room temperature for 1 hour and then allowed to stand at 170 ℃ for crystallization for 3 days. And (3) separating the mother solution after crystallization to obtain a solid, washing the solid with deionized water to be neutral, drying, roasting for 6 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve nanosheet, wherein an XRD (X-ray diffraction) diagram of the molecular sieve nanosheet is similar to that shown in figure 1, and an SEM (scanning Electron microscope) diagram shows that the thickness of the nanosheet is 5-50nm, and the particle size is 500-800 nm. The molecular sieve had a Si/Al molar ratio of 0.02.
0.50 g of prepared ZnCrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 1.
[ example 2 ]
ZnCrOxMixed oxides were prepared as in [ example 1 ].
The sheet SAPO molecular sieve is prepared by the following steps:
5.1 g of isopropyl alcohol aluminum powder and 1.7 g of pseudo-boehmite (Al)2 O 340% by weight) was dispersed in 59.9 g of tetraethylammonium hydroxide (TEAOH, 25% by weight) solution and dispersed with stirringHomogenizing; 11.6 g of phosphoric acid (85 wt% in concentration) was added to the above solution, and stirring was continued at room temperature; 0.15 g of silica Sol (SiO)240 wt%) was added to the above solution, stirred at room temperature for 1 hour and then allowed to stand at 170 ℃ for crystallization for 3 days. And (3) separating the mother solution after crystallization to obtain a solid, washing the solid with deionized water to be neutral, drying, roasting for 6 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve nanosheet, wherein an XRD (X-ray diffraction) diagram of the molecular sieve nanosheet is similar to that shown in figure 1, and an SEM (scanning Electron microscope) diagram shows that the thickness of the nanosheet is 20-50nm, and the particle size is 800 nm. The molecular sieve had a Si/Al molar ratio of 0.02.
0.50 g of prepared ZnCrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 1.
[ example 3 ]
ZnCrOxMixed oxides were prepared as in [ example 1 ].
The sheet SAPO molecular sieve is prepared by the following steps:
10.2 g of aluminum isopropoxide powder was dispersed in 59.9 g of tetraethylammonium hydroxide (TEAOH, 25 wt% strength) solution and stirred until completely dissolved; 11.6 g of phosphoric acid (85 wt% in concentration) was added to the above solution, and stirring was continued at room temperature; 0.37 g of silica Sol (SiO)240 wt%) was added to the above solution, stirred at room temperature for 1 hour and then allowed to stand at 170 ℃ for crystallization for 3 days. And (3) separating the mother solution after crystallization to obtain a solid, washing the solid with deionized water to be neutral, drying, roasting for 6 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve nanosheet, wherein an XRD (X-ray diffraction) diagram of the molecular sieve nanosheet is similar to that shown in figure 1, and an SEM (scanning Electron microscope) diagram shows that the thickness of the nanosheet is 10-50nm and the particle size is 500-800 nm. The molecular sieve had a Si/Al molar ratio of 0.05.
0.50 g of prepared ZnCrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) is introduced intoThe reaction mixture enters a catalytic bed for reaction in a reaction tube, the reaction temperature is 390 ℃, the pressure of a reaction system is 4MPa, and the gas volume space velocity is 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 1.
[ example 4 ]
ZnCrOxMixed oxides were prepared as in [ example 1 ].
The sheet SAPO molecular sieve is prepared by the following steps:
10.2 g of aluminum isopropoxide powder was dispersed in 59.9 g of tetraethylammonium hydroxide (TEAOH, 25 wt% strength) solution and stirred until completely dissolved; 11.6 g of phosphoric acid (85 wt% in concentration) was added to the above solution, and stirring was continued at room temperature; 0.75 g of silica Sol (SiO)240 wt%) was added to the above solution, stirred at room temperature for 1 hour and then allowed to stand at 170 ℃ for crystallization for 3 days. And (3) separating the mother liquor to obtain a solid after crystallization, washing the solid with deionized water to be neutral, drying, and roasting for 6 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve nanosheet. The XRD pattern and scanning electron microscope image of the obtained molecular sieve are shown in FIG. 1 and FIG. 2. As can be seen from FIG. 1, the molecular sieve is SAPO-34. The molecular sieve had a Si/Al molar ratio of 0.10.
0.50 g of prepared ZnCrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 1.
[ example 5]
ZnCrOxMixed oxides were prepared as in [ example 1 ].
The sheet SAPO molecular sieve is prepared by the following steps:
dispersing 10.2 g of aluminum isopropoxide powder in 10.6 g of triethylamine, and stirring until the aluminum isopropoxide powder is completely dissolved; 11.6 g of phosphoric acid (85 wt% in concentration) was added to the above solution, and stirring was continued at room temperature; 0.37 g of silica Sol (SiO)240 wt.%) was added to the above solution, chamberStirred for 1 hour at the temperature and then kept stand for crystallization for 3 days at 170 ℃. And (3) separating the mother solution after crystallization to obtain a solid, washing the solid with deionized water to be neutral, drying the solid, roasting the solid for 6 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve nanosheet, wherein an XRD (X-ray diffraction) diagram of the molecular sieve nanosheet is similar to that shown in figure 1, and an SEM (scanning Electron microscope) diagram shows that the thickness of the nanosheet is below 30nm and the particle size is 600-800 nm. The molecular sieve had a Si/Al molar ratio of 0.05.
0.50 g of prepared ZnCrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 1.
[ example 6 ]
ZnCrOxMixed oxides were prepared as in [ example 1 ].
The sheet SAPO molecular sieve is prepared by the following steps:
10.2 g of aluminum isopropoxide powder was dispersed in 59.9 g of tetraethylammonium hydroxide (TEAOH, 25 wt% strength) solution and stirred until completely dissolved; 11.6 g of phosphoric acid (85 wt% in concentration) was added to the above solution, and stirring was continued at room temperature; 1.5 g of silica Sol (SiO)240 wt%) was added to the above solution, stirred at room temperature for 1 hour and then allowed to stand at 170 ℃ for crystallization for 3 days. And (3) separating the mother solution after crystallization to obtain a solid, washing the solid with deionized water to be neutral, drying, roasting for 6 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve nanosheet, wherein an XRD (X-ray diffraction) diagram of the molecular sieve nanosheet is similar to that shown in figure 1, and an SEM (scanning Electron microscope) diagram shows that the thickness of the nanosheet is 30-50nm and the particle size is 500-800 nm. The molecular sieve had a Si/Al molar ratio of 0.20.
0.50 g of prepared ZnCrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1Preparation of low-carbon olefin by synthesis gas under conditionAnd (4) reacting. The reaction results are shown in Table 1.
[ example 7 ]
ZnAlOxPreparation of mixed oxides:
weighing a certain amount of Al (NO)3)2·9H2O and Zn (NO)3)2·6H2Dispersing the solid O in water, and stirring until the solid O is completely dissolved; weighing a certain amount of (NH)4)2CO3The solid was dissolved in water to prepare a 0.1M solution. Dropping the two aqueous solutions into a beaker at the same time for coprecipitation, filtering and washing the precipitate, drying the precipitate at 100 ℃ overnight, and roasting the precipitate at 500 ℃ for 4 h.
SAPO molecular sieves were prepared as in [ example 3 ].
0.50 g of prepared ZnAlOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 2.
[ example 8 ]
ZnZrOxPreparation of mixed oxides:
weighing a certain amount of Zr (NO)3)2·5H2O and Zn (NO)3)2·6H2Dispersing the solid O in water, and stirring until the solid O is completely dissolved; weighing a certain amount of (NH)4)2CO3The solid was dissolved in water to prepare a 0.1M solution. Dropping the two aqueous solutions into a beaker at the same time for coprecipitation, filtering and washing the precipitate, drying the precipitate at 100 ℃ overnight, and roasting the precipitate at 500 ℃ for 4 h.
SAPO molecular sieves were prepared as in [ example 3 ].
0.50 g of prepared ZnZrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalytic bedThe reaction temperature is 390 ℃, the pressure of the reaction system is 4MPa, and the gas volume space velocity is 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 2.
[ example 9 ]
InZrOxThe mixed oxide is prepared by the following steps:
weighing a certain amount of In (NO)3)3And Zr (NO)3)2·5H2Dispersing the solid O in water, and stirring until the solid O is completely dissolved; weighing a certain amount of (NH)4)2CO3The solid was dissolved in water to prepare a 0.1M solution. Dropping the two aqueous solutions into a beaker at the same time for coprecipitation, filtering and washing the precipitate, drying the precipitate at 100 ℃ overnight, and roasting the precipitate at 500 ℃ for 4 h.
SAPO molecular sieves were prepared as in [ example 3 ].
0.50 g of prepared InZrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 2.
[ example 10 ]
ZnCrOxMixed oxides were prepared as in [ example 1 ].
SAPO molecular sieves were prepared as in [ example 3 ].
0.60 g of prepared ZnCrOxMixing the mixed oxide with 0.40 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 3.
[ example 11 ]
ZnCrOxMixed oxidesPrepared as in [ example 1 ].
SAPO molecular sieves were prepared as in [ example 3 ].
0.50 g of prepared ZnCrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 9,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 3.
[ example 12 ]
ZnCrOxMixed oxides were prepared as in [ example 1 ].
SAPO molecular sieves were prepared as in [ example 3 ].
0.50 g of prepared ZnCrOxMixing the mixed oxide with 0.50 g of SAPO molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 6MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 3.
Comparative example 1
According to the literature [ Science,2016,351,1065]Preparation method of (1), Synthesis of Zn3.5CrAl oxide and SAPO-34 molecular sieve. The SAPO-34 molecular sieve is of a micron cubic structure, the particle size is about 2 microns, and the Si/Al molar ratio of the molecular sieve is 0.24.
0.50 g of Zn3.5CrAl was mixed with 0.50 g SAPO-34, and charged into a quartz reaction tube having an inner diameter of 6 mm to mix (n)Hydrogen gas：nCarbon monoxide50: 50) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 4.
Comparative example 2
According to the literature [ Angewandte Chemie,2016,128,4803]Preparation method of (1), synthesis of ZnZrOxAnd SAPO-34. The SAPO-34 molecular sieve is of a micron cubic structure, the particle size is about 2.5 microns, and the Si/Al molar ratio of the molecular sieve is 0.05.
0.50 g of ZnZr2Mixed with 0.50 g of SAPO-34, and packed in a quartz reaction tube having an inner diameter of 6 mm to mix (n)Hydrogen gas：nCarbon monoxide50: 50) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 4.
Comparative example 3
According to the preparation method of the patent [ CN103157489A ], the FeMnCuK catalyst is synthesized.
1.50 g of FeMnCuK catalyst was charged into a quartz reaction tube having an inner diameter of 6 mm, and (n) was introducedHydrogen gas：nCarbon monoxide50: 50) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 4.
Comparative example 4
ZnCrOxMixed oxides were prepared as in [ example 1 ].
According to the preparation method of the literature [ Chemical Engineering Journal,2017,323,295], a micron SAPO-18/34 intergrown molecular sieve is synthesized, and the scanning electron microscope map of the micron SAPO-18/34 intergrown molecular sieve is shown in FIG. 3. The particle size is about 2.5 microns, the particles are cubic or columnar, and the Si/Al molar ratio of the molecular sieve is 0.05.
0.50 g of prepared ZnCrOxMixing the mixed oxide with 0.50 g of prepared micron SAPO-18/34 intergrowth molecular sieve, loading into a quartz reaction tube with an inner diameter of 6 mm, and reacting (n)Hydrogen gas：nCarbon monoxide1:1) introducing into a reaction tube, reacting in a catalyst bed at 390 deg.C under 4MPa and gas volume space velocity of 6,000h-1The reaction for preparing the low-carbon olefin from the synthesis gas is carried out under the condition. The reaction results are shown in Table 4.
TABLE 1
Catalyst and process for preparing same Conversion/wt.% C2-4 olefin Selectivity/wt%
Example 1 ZnCrOx+ SAPO-34 (weight ratio 1:1) 25.3 85.6
Example 2 ZnCrOx+ SAPO-34 (weight ratio 1:1) 24.1 83.1
Example 3 ZnCrOx+ SAPO-34 (weight ratio 1:1) 32.8 80.5
Example 4 ZnCrOx+ SAPO-34 (weight ratio 1:1) 33.0 78.1
Example 5 ZnCrOx+ SAPO-34 (weight ratio 1:1) 29.1 79.8
Example 6 ZnCrOx+ SAPO-34 (weight ratio 1:1) 32.8 76.8
TABLE 2
Figure BDA0002238815120000141
TABLE 3
Figure BDA0002238815120000151
TABLE 4
Figure BDA0002238815120000152

Claims (10)

1. A catalyst for preparing low-carbon olefin from synthetic gas comprises metal oxide and SAPO molecular sieve, wherein the SAPO molecular sieve is sheet-shaped and has a thickness of less than 100 nm.
2. The catalyst of claim 1, wherein: the particle size of the SAPO molecular sieve is below 1000 nm.
3. A catalyst according to claim 1 or 2, wherein: the SAPO molecular sieve has a Si/Al molar ratio of 0.001-0.20, preferably 0.01-0.15, more preferably 0.02-0.10.
4. The catalyst of claim 1, wherein: the SAPO molecular sieve is an SAPO-34 molecular sieve.
5. The catalyst of claim 1, wherein: the metal oxide is selected from one or more of zinc oxide, zinc-chromium mixed oxide, zinc-zirconium mixed oxide, zinc-aluminum mixed oxide, indium oxide, zirconium oxide, indium-zirconium mixed oxide, manganese-chromium mixed oxide, manganese-aluminum mixed oxide, manganese-zirconium mixed oxide, cobalt-aluminum mixed oxide, iron-aluminum mixed oxide and cerium oxide.
6. The catalyst of claim 1, wherein: the metal oxide is selected from one or more of zinc-chromium mixed oxide, zinc-zirconium mixed oxide, zinc-aluminum mixed oxide and indium-zirconium mixed oxide.
7. The catalyst of claim 1, wherein: the mass ratio of the metal oxide to the SAPO molecular sieve is 1: 8-8: 1, preferably 1: 2-2: 1.
8. the catalyst of claim 1, wherein: the metal oxide and the SAPO molecular sieve are present independently of each other.
9. A method for preparing low-carbon olefin by using synthesis gas is characterized by comprising the following steps: the synthesis gas contacts with the catalyst of any one of claims 1 to 8 to react to obtain a product containing low-carbon olefin.
10. The method of claim 9, wherein: the reaction conditions were as follows: the reaction temperature is 320-500 ℃, the reaction pressure is 0.5-8MPa, and the volume space velocity is 1000-9600h-1In syngas, CO and H2The volume ratio of (A) to (B) is 0.3 to 3.5.
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CN103641131A (en) * 2013-12-10 2014-03-19 吉林大学 Slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, preparation method and application thereof
CN104190465A (en) * 2014-09-05 2014-12-10 福州大学 SAPO-5 molecular sieve loaded metal oxide photocatalyst
CN107971026A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 Combination catalyst for producing light olefins
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CN109701628A (en) * 2017-10-26 2019-05-03 中国石油化工股份有限公司 Composite catalyst containing phosphate aluminium molecular sieve and its application in one-step method from syngas alkene
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CN102616810A (en) * 2012-04-17 2012-08-01 吉林大学 Cubic or sheet-shaped nano SAPO-34 molecular sieve and application thereof
CN103641131A (en) * 2013-12-10 2014-03-19 吉林大学 Slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, preparation method and application thereof
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